Ziegler-Natta—metallocene dual catalyst systems with activator-supports

ABSTRACT

Catalyst systems having both a metallocene catalyst component and a Ziegler-Natta component are disclosed. Such catalyst systems can contain a metallocene compound, an activator-support, an organoaluminum compound, and a Ziegler-Natta component comprising titanium supported on magnesium chloride.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 62/189,770, filed on Jul. 8, 2015, the disclosure of which isincorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.In some end-use applications, it can be beneficial to use a catalystsystem having both a Ziegler-type catalyst component and a metallocenecatalyst component to produce polymers having high molecular weights andbroad molecular weight distributions. Accordingly, it is to these endsthat the present invention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, the present invention relates to methodsfor preparing dual catalyst compositions, and to the resultant catalystcompositions. Catalyst compositions of the present invention can be usedto produce, for example, ethylene-based homopolymers and copolymers fora variety of end-use applications.

Various processes and methods related to the preparation of catalystcompositions are disclosed herein. In one aspect, a process forproducing a catalyst composition is disclosed, and in this aspect, theprocess can comprise contacting, in any order, (i) a metallocenecompound, (ii) a Ziegler-Natta component comprising titanium supportedon MgCl₂, (iii) an activator-support, and (iv) an organoaluminumcompound, to produce the catalyst composition. In another aspect, aprocess for producing a catalyst composition is disclosed, and in thisaspect, the process can comprise (a) contacting an activator-support andan organoaluminum compound for a first period of time to form aprecontacted mixture, and (b) contacting the precontacted mixture with ametallocene compound and a Ziegler-Natta component comprising titaniumsupported on MgCl₂ for a second period of time to form the catalystcomposition.

Catalyst compositions also are encompassed by the present invention. Inone aspect, the catalyst composition can comprise (i) a metallocenecompound, (ii) a Ziegler-Natta component comprising titanium supportedon MgCl₂, (iii) an activator-support, and (iv) an organoaluminumcompound. In another aspect, the catalyst composition can comprise (A) aprecontacted mixture comprising an activator-support and anorganoaluminum compound, (B) a metallocene compound, and (C) aZiegler-Natta component comprising titanium supported on MgCl₂.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer. Generally, the catalystcomposition employed can comprise any of the multicomponent catalystsystems disclosed herein, for instance, any of the metallocenecompounds, any of the Ziegler-Natta components, any ofactivator-supports, and any of the organoaluminum compounds disclosedherein.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer (e.g., an ethylene homopolymer orcopolymer) consistent with aspects of this invention can becharacterized as having the following properties: a melt index of lessthan or equal to about 15 g/10 min, a ratio of Mw/Mn in a range fromabout 2 to about 15, and a density in a range from about 0.89 g/cm³ toabout 0.96 g/cm³. Another illustrative and non-limiting example of anolefin polymer of the present invention can have a high load melt indexof less than or equal to about 150 g/10 min, a ratio of Mw/Mn in a rangefrom about 2.5 to about 15, and a density in a range from about 0.89g/cm³ to about 0.96 g/cm³. These polymers, in further aspects, can becharacterized by low levels of long chain branches (LCB), and/or by adecreasing or substantially constant short chain branch distribution(SCBD). In some aspects, the polymer (e.g., an ethylene/α-olefincopolymer) can be characterized by less than about 4 wt. % of thepolymer eluted below a temperature of 40° C. in an ATREF test, and/or byfrom about 40 to about 62 wt. % of the polymer eluted between 40 and 76°C. in an ATREF test, and/or by from about 2 to about 21 wt. % of thepolymer eluted between 76 and 86° C. in an ATREF test, and/or by fromabout 29 to about 40 wt. % of the polymer eluted above a temperature of86° C. in an ATREF test. In other aspects, the polymer (e.g., anethylene/α-olefin copolymer) can be characterized by from about 1 toabout 18 wt. % (or from about 1 to about 16 wt. %) of the polymer elutedbelow a temperature of 40° C. in an ATREF test, by from about 1 to about15 wt. % (or from about 1 to about 10 wt. %) of the polymer elutedbetween 76 and 86° C. in an ATREF test, by from about 27 to about 60 wt.% (or from about 29 to about 60 wt. %) of the polymer eluted above atemperature of 86° C. in an ATREF test, and the remainder of the polymer(to reach 100 wt. %) eluted between 40 and 76° C. in an ATREF test.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects may bedirected to various feature combinations and sub-combinations describedin the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distributions of thepolymers of Examples 1-2 and 8.

FIG. 2 presents a plot of the molecular weight distributions of thepolymers of Examples 10, 12, and 17.

FIG. 3 presents a plot of the molecular weight distributions of thepolymers of Examples 19-20 and 26.

FIG. 4 presents a plot of the molecular weight distributions of thepolymers of Examples 33-34 and 39.

FIG. 5 presents a plot of the molecular weight distributions of thepolymers of Examples 40-41 and 43.

FIG. 6 presents a plot of the ATREF profiles of the polymers of Examples7, 10, and 44.

FIG. 7 presents a plot of the ATREF profile of the polymer of Example45.

FIG. 8 presents a plot of the ATREF profile of the polymer of Example46.

FIG. 9 presents a plot of the ATREF profile of the polymer of Example47.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter can be described such that,within particular aspects, a combination of different features can beenvisioned. For each and every aspect and each and every featuredisclosed herein, all combinations that do not detrimentally affect thedesigns, compositions, processes, and/or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect and/or feature disclosed herein can be combined to describeinventive polymers, processes, and compositions consistent with thepresent disclosure.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) a metallocene compound, (ii) a Ziegler-Natta componentcomprising titanium supported on MgCl₂, (iii) an activator-support, and(iv) an organoaluminum compound.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

Unless otherwise specified, the term “substituted” when used to describea group, for example, when referring to a substituted analog of aparticular group, is intended to describe any non-hydrogen moiety thatformally replaces a hydrogen in that group, and is intended to benon-limiting. Also, unless otherwise specified, a group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Moreover, unless otherwise specified, “substituted” is intended to benon-limiting and include inorganic substituents or organic substituentsas understood by one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen, whethersaturated or unsaturated. Other identifiers can be utilized to indicatethe presence of particular groups in the hydrocarbon (e.g., halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon).The term “hydrocarbyl group” is used herein in accordance with thedefinition specified by IUPAC: a univalent group formed by removing ahydrogen atom from a hydrocarbon (that is, a group containing onlycarbon and hydrogen). Non-limiting examples of hydrocarbyl groupsinclude alkyl, alkenyl, aryl, and aralkyl groups, amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth, as well as alloysand blends thereof. The term “polymer” also includes all possiblegeometrical configurations, unless stated otherwise, and suchconfigurations can include isotactic, syndiotactic, and randomsymmetries. The term “polymer” also includes impact, block, graft,random, and alternating copolymers. A copolymer is derived from anolefin monomer and one olefin comonomer, while a terpolymer is derivedfrom an olefin monomer and two olefin comonomers. Accordingly, “polymer”encompasses copolymers, terpolymers, etc., derived from any olefinmonomer and comonomer(s) disclosed herein. Similarly, an ethylenepolymer would include ethylene homopolymers, ethylene copolymers,ethylene terpolymers, and the like. As an example, an olefin copolymer,such as an ethylene copolymer, can be derived from ethylene and acomonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer andcomonomer were ethylene and 1-hexene, respectively, the resultingpolymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands can include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene may be referred to simply as the “catalyst,” in much thesame way the term “co-catalyst” may be used herein to refer to, forexample, an organoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic sites, or the fate of the organoaluminum compound,the metallocene compound, the Ziegler-Natta component, or theactivator-support, after combining these components. Therefore, theterms “catalyst composition,” “catalyst mixture,” “catalyst system,” andthe like, encompass the initial starting components of the composition,as well as whatever product(s) may result from contacting these initialstarting components, and this is inclusive of both heterogeneous andhomogenous catalyst systems or compositions. The terms “catalystcomposition,” “catalyst mixture,” “catalyst system,” and the like, maybe used interchangeably throughout this disclosure.

The terms “contact product,” “contacting,” and the like, are used hereinto describe methods and compositions wherein the components are combinedor contacted together in any order, in any manner, and for any length oftime, unless otherwise specified. For example, the components can becontacted by blending or mixing. Further, unless otherwise specified,the contacting of any component can occur in the presence or absence ofany other component of the methods and compositions described herein.Combining additional materials or components can be done by any suitablemethod. A contact product encompasses mixtures, blends, solutions,slurries, reaction products, and the like, as well as combinationsthereof. Similarly, the contacting of components refers to materialswhich can be blended, mixed, slurried, dissolved, reacted, treated, orotherwise contacted in some other manner.

A “precontacted mixture” describes a mixture of catalyst components thatare combined or contacted for a period of time prior to being contactedwith other catalyst components. According to this description, it ispossible for the components of the precontacted mixture, once contacted,to have reacted to form at least one chemical compound, formulation,species, or structure different from the distinct initial compounds orcomponents used to prepare the precontacted mixture.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the ratio of Mw/Mnof an olefin polymer produced in an aspect of this invention. By adisclosure that the Mw/Mn can be in a range from about 3 to about 12,Applicants intend to recite that the Mw/Mn can be any ratio in the rangeand, for example, can be equal to about 3, about 4, about 5, about 6,about 7, about 8, about 9, about 10, about 11, or about 12.Additionally, the Mw/Mn can be within any range from about 3 to about 12(for example, from about 3.5 to about 10.5), and this also includes anycombination of ranges between about 3 and about 12 (for example, theMw/Mn can be in a range from about 3 to about 8, or from about 9 toabout 12). Likewise, all other ranges disclosed herein should beinterpreted in a manner similar to these examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto catalyst compositions containing a Ziegler-Natta component and ametallocene component, to polymerization processes utilizing suchcatalyst compositions, and to the resulting olefin polymers producedfrom the polymerization processes. While not wishing to be bound by thefollowing theory, it is believed that the polymers disclosed herein, dueto a specific combination of polymer characteristics (e.g., density,melt flow, molecular weight, and ATREF features), have improvedtoughness and tear resistance, making them particularly suitable forfilm, sheet, and other demanding end-use applications.

Activator-supports

The present invention encompasses various catalyst compositionscontaining an activator-support, and various methods of preparingcatalyst compositions using an activator-support. In one aspect, theactivator-support can comprise a solid oxide treated with anelectron-withdrawing anion. Alternatively, in another aspect, theactivator-support can comprise a solid oxide treated with anelectron-withdrawing anion, the solid oxide containing a Lewis-acidicmetal ion. Non-limiting examples of suitable activator-supports aredisclosed in, for instance, U.S. Pat. Nos. 7,294,599, 7,601,665,7,884,163, 8,309,485, and 9,023,959, which are incorporated herein byreference in their entirety.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form an activator-support, eithersingly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, and the like. The solid oxideused herein also can encompass oxide materials such as silica-coatedalumina, as described in U.S. Pat. No. 7,884,163.

Accordingly, in one aspect, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, silica-titania,zirconia, silica-zirconia, magnesia, bona, zinc oxide, any mixed oxidethereof, or any combination thereof. In another aspect, the solid oxidecan comprise alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania,silica-titania, zirconia, silica-zirconia, magnesia, boria, or zincoxide, as well as any mixed oxide thereof, or any mixture thereof. Inanother aspect, the solid oxide can comprise silica, alumina, titania,zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or anycombination thereof. In yet another aspect, the solid oxide can comprisesilica-alumina, silica-coated alumina, silica-titania, silica-zirconia,alumina-boria, or any combination thereof. In still another aspect, thesolid oxide can comprise alumina, silica-alumina, silica-coated alumina,or any mixture thereof; alternatively, alumina; alternatively,silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have a silica content from about 5 to about 95% byweight. In one aspect, the silica content of these solid oxides can befrom about 10 to about 80%, or from about 20% to about 70%, silica byweight. In another aspect, such materials can have silica contentsranging from about 15% to about 60%, or from about 25% to about 50%,silica by weight. The solid oxides contemplated herein can have anysuitable surface area, pore volume, and particle size, as would berecognized by those of skill in the art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspect,the electron-withdrawing component can be an electron-withdrawing anionderived from a salt, an acid, or other compound, such as a volatileorganic compound, that serves as a source or precursor for that anion.Examples of electron-withdrawing anions can include, but are not limitedto, sulfate, bisulfate, fluoride, chloride, bromide, iodide,fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, tungstate, molybdate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsalso can be employed. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, and the like, or any combinationthereof, in some aspects provided herein. In other aspects, theelectron-withdrawing anion can comprise sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof. Yet, in otheraspects, the electron-withdrawing anion can comprise fluoride and/orsulfate.

The activator-support generally can contain from about 1 to about 25 wt.% of the electron-withdrawing anion, based on the weight of theactivator-support. In particular aspect aspects provided herein, theactivator-support can contain from about 1 to about 20 wt. %, from about2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 toabout 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12wt. %, or from about 4 to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the activator-support.

In an aspect, the activator-support can comprise fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, phosphatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, phosphated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, fluorided-chlorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, as well as any mixture or combination thereof. Inanother aspect, the activator-support employed in the processes andcatalyst systems described herein can be, or can comprise, a fluoridedsolid oxide and/or a sulfated solid oxide and/or a phosphated solidoxide, non-limiting examples of which can include fluorided alumina,sulfated alumina, phosphated alumina, fluorided silica-alumina, sulfatedsilica-alumina, phosphated silica-alumina, fluorided silica-zirconia,fluorided silica-coated alumina, fluorided-chlorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, as well as combinations thereof. In yet anotheraspect, the activator-support can comprise fluorided alumina;alternatively, chlorided alumina; alternatively, sulfated alumina;alternatively, phosphated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,phosphated silica-alumina; alternatively, fluorided silica-zirconia;alternatively, chlorided silica-zirconia; alternatively, sulfatedsilica-coated alumina; alternatively, phosphated silica-coated alumina;alternatively, fluorided-chlorided silica-coated alumina; oralternatively, fluorided silica-coated alumina.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metal ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, or phosphatedsolid oxides) are well known to those of skill in the art.

Organoaluminum Compounds

The present invention encompasses various catalyst compositionscontaining an organoaluminum compound, and various methods of preparingcatalyst compositions using an organoaluminum compound. More than oneorganoaluminum compound can be used. For instance, a mixture orcombination of two suitable organoaluminum compounds can be used in theprocesses and catalyst systems disclosed herein.

In some aspects, suitable organoaluminum compounds can have the formula,(R^(Z))₃Al, wherein each R^(Z) independently can be an aliphatic grouphaving from 1 to 10 carbon atoms. For example, each R^(Z) independentlycan be methyl, ethyl, propyl, butyl, hexyl, or isobutyl. In otheraspects, suitable organoaluminum compounds can have the formula,Al(X⁷)_(m)(X⁸)_(3−m), wherein each X⁷ independently can be ahydrocarbyl; each X⁸ independently can be an alkoxide or an aryloxide, ahalide, or a hydride; and m can be from 1 to 3, inclusive. Hydrocarbylis used herein to specify a hydrocarbon radical group and includes, forinstance, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl,cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups. Inone aspect, each X⁷ independently can be any hydrocarbyl having from 1to about 18 carbon atoms, or from 1 to about 8 carbon atoms, or an alkylhaving from 1 to 10 carbon atoms. For example, each X⁷ independently canbe methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, andthe like, in certain aspects of the present invention. According toanother aspect of the present invention, each X⁸ independently can be analkoxide or an aryloxide, any one of which has from 1 to 18 carbonatoms, a halide, or a hydride. In yet another aspect of the presentinvention, each X⁸ can be selected independently from fluorine andchlorine. In the formula, Al(X⁷)_(m)(X⁸)_(3−m), m can be a number from 1to 3 (inclusive) and typically, m can be 3. The value of m is notrestricted to be an integer; therefore, this formula can includesesquihalide compounds or other organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention can include, but are not limited to,trialkylaluminum compounds, dialkylaluminum halide compounds,dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds,and combinations thereof. Specific non-limiting examples of suitableorganoaluminum compounds can include trimethylaluminum (TMA),triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum(TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethyl aluminumethoxide, diethyl aluminum chloride, and the like, or combinationsthereof. In one aspect, an organoaluminum compound used in the processesand catalyst systems disclosed herein can comprise (or consistessentially of, or consist of) triethylaluminum (TEA), while in anotheraspect, an organoaluminum compound used in the processes and catalystsystems disclosed herein can comprise (or consist essentially of, orconsist of) triisobutylaluminum (TIBA). Yet, in another aspect, amixture of TEA and TIBA can be used as the organoaluminum component inthe processes described herein (or as the organoaluminum component inthe catalyst systems disclosed herein).

Metallocene Compounds

Catalyst compositions consistent with this invention can contain abridged metallocene compound or an unbridged metallocene compound. Themetallocene compound can comprise, for example, a transition metal (oneor more than one) from Groups 3-12 of the Periodic Table of theElements. In one aspect, the metallocene compound can comprise a Group3, 4, 5, or 6 transition metal, or a combination of two or moretransition metals. The metallocene compound can comprise chromium,titanium, zirconium, hafnium, vanadium, or a combination thereof, or cancomprise titanium, zirconium, hafnium, or a combination thereof, inother aspects. Accordingly, the metallocene compound can comprisetitanium, or zirconium, or hafnium, either singly or in combination.

In some aspects of this invention, the metallocene compound can comprisean unbridged metallocene compound, for instance, an unbridged zirconiumor hafnium based metallocene compound and/or an unbridged zirconiumand/or hafnium based dinuclear metallocene compound. In one aspect, themetallocene compound can comprise an unbridged zirconium or hafniumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group. In anotheraspect, the metallocene compound can comprise an unbridged zirconium orhafnium based metallocene compound containing two cyclopentadienylgroups. In yet another aspect, the metallocene compound can comprise anunbridged zirconium or hafnium based metallocene compound containing twoindenyl groups. In still another aspect, the metallocene compound cancomprise an unbridged zirconium or hafnium based metallocene compoundcontaining a cyclopentadienyl and an indenyl group.

In some aspects, the metallocene compound can comprise an unbridgedzirconium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group,while in other aspects, the metallocene compound can comprise adinuclear unbridged metallocene compound with an alkenyl linking group.

The metallocene compound can comprise, in particular aspects of thisinvention, an unbridged metallocene compound having formula (I):

Within formula (I), M, Cp^(A), Cp^(B), and each X are independentelements of the unbridged metallocene compound. Accordingly, theunbridged metallocene compound having formula (I) can be described usingany combination of M, Cp^(A), Cp^(B), and X disclosed herein.

Unless otherwise specified, formula (I) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

In accordance with aspects of this invention, the metal in formula (I),M, can be Ti, Zr, or Hf. In one aspect, for instance, M can be Zr or Hf,while in another aspect, M can be Ti; alternatively, M can be Zr; oralternatively, M can be Hf.

Each X in formula (I) independently can be a monoanionic ligand. In someaspects, suitable monoanionic ligands can include, but are not limitedto, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group, —OBR¹₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR¹ ₂, or OSO₂R¹, wherein R¹is a C₁ to C₁₈ hydrocarbyl group. In another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group, aC₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, a C₁to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R₁, wherein R¹ is a C₁ to C₁₂ hydrocarbyl group. Inanother aspect, each X independently can be H, BH₄, a halide, a C₁ toC₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ to C₁₀hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ to C₁₀hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R′, wherein R¹ is a C₁ toC₁₀ hydrocarbyl group. In yet another aspect, each X independently canbe H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, a C₁ to C₈hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR¹ ₂,or OSO₂R¹, wherein R¹ is a C₁ to C₈ hydrocarbyl group. In still anotheraspect, each X independently can be a halide or a C₁ to C₁₈ hydrocarbylgroup. For example, each X can be Cl.

The hydrocarbyl group which can be an X in formula (I) can be a C₁ toC₃₆ hydrocarbyl group, including, but not limited to, a C₁ to C₃₆ alkylgroup, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkyl group, a C₆ toC₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. For instance, each Xindependently can be a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group,a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈aralkyl group; alternatively, each X independently can be a C₁ to C₁₂alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂ cycloalkyl group, aC₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group; alternatively, eachX independently can be a C₁ to C₁₀ alkyl group, a C₂ to C₁₀ alkenylgroup, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group, or a C₇ toC₁₀ aralkyl group; or alternatively, each X independently can be a C₁ toC₅ alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, aC₆ to C₈ aryl group, or a C₇ to C₈ aralkyl group.

Accordingly, in some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (I) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one aspect, each X in formula (I)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another aspect,each X in formula (I) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another aspect, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (I) can be a cycloalkyl group, including, but notlimited to, a cyclobutyl group, a substituted cyclobutyl group, acyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group,a substituted cyclohexyl group, a cycloheptyl group, a substitutedcycloheptyl group, a cyclooctyl group, or a substituted cyclooctylgroup. For example, an X in formula (I) can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. Moreover, each X in formula (I) independently can be acyclobutyl group or a substituted cyclobutyl group; alternatively, acyclopentyl group or a substituted cyclopentyl group; alternatively, acyclohexyl group or a substituted cyclohexyl group; alternatively, acycloheptyl group or a substituted cycloheptyl group; alternatively, acyclooctyl group or a substituted cyclooctyl group; alternatively, acyclopentyl group; alternatively, a substituted cyclopentyl group;alternatively, a cyclohexyl group; or alternatively, a substitutedcyclohexyl group. Substituents which can be utilized for the substitutedcycloalkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted cycloalkyl groupwhich can be an X in formula (I).

In some aspects, the aryl group which can be an X in formula (I) can bea phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an aspect, the aryl group can be a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (I).

In an aspect, the substituted phenyl group which can be an X in formula(I) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X group(s) in formula (I).

In some aspects, the aralkyl group which can be an X group in formula(I) can be a benzyl group or a substituted benzyl group. In an aspect,the aralkyl group can be a benzyl group or, alternatively, a substitutedbenzyl group. Substituents which can be utilized for the substitutedaralkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted aralkyl groupwhich can be an X group(s) in formula (I).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (I) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (I). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be an X in formula (I) can include, but are not limited to, amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an aspect, the hydrocarboxy group which can be an X informula (I) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (I)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl groupwhich can be an X in formula (I) can be, for instance, a methylaminylgroup (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), an n-propylaminylgroup (—NHCH₂CH₂CH₃), an iso-propylaminyl group (—NHCH(CH₃)₂), ann-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group(—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be an X in formula (I) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, each X independentlycan be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively, a C₁ to C₂₄hydrocarbylsilyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₈ hydrocarbylsilyl group. In anaspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group canbe any hydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group,a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ arylgroup, a C₇ to C₈ aralkyl group, etc.). As used herein, hydrocarbylsilylis intended to cover (mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl(—SiHR₂), and trihydrocarbylsilyl (—SiR₃) groups, with R being ahydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C₃to C₃₆ or a C₃ to C₁₈ trihydrocarbylsilyl group, such as, for example, atrialkylsilyl group or a triphenylsilyl group. Illustrative andnon-limiting examples of hydrocarbylsilyl groups which can be an Xgroup(s) in formula (I) can include, but are not limited to,trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl),tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, andthe like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X can include, but are notlimited to —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be X can compriseup to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₂, orC₁ to C₈ hydrocarbylaminylsilyl groups). In an aspect, each hydrocarbyl(one or more) of the hydrocarbylaminylsilyl group can be any hydrocarbylgroup disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂ to C₅ alkenylgroup, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, a C₇ to C₈aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl is intended tocover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂, —N(SiHR₂)₂, and—N(SiR₃)₂ groups, among others, with R being a hydrocarbyl group.

In an aspect, each X independently can be —OBR¹ ₂ or —OSO₂R₁, wherein R¹is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁ to C₁₈hydrocarbyl group. The hydrocarbyl group in OBR¹ ₂ and/or OSO₂R¹independently can be any hydrocarbyl group disclosed herein, such as,for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₄to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈ aralkylgroup; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenylgroup, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ toC₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or aC₇ to C₈ aralkyl group.

In one aspect, each X independently can be H, BH₄, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, each X can be H;alternatively, F; alternatively, Cl; alternatively, Br; alternatively,I; alternatively, BH₄; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, a C₁ toC₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₁₈ hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (I), Cp^(A) and Cp^(B) independently can be a substituted orunsubstituted cyclopentadienyl or indenyl group. In one aspect, Cp^(A)and Cp^(B) independently can be an unsubstituted cyclopentadienyl orindenyl group. Alternatively, Cp^(A) and Cp^(B) independently can be asubstituted indenyl or cyclopentadienyl group, for example, having up to5 substituents.

If present, each substituent on Cp^(A) and Cp^(B) independently can beH, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. Importantly, each substituent on Cp^(A) and/orCp^(B) can be either the same or a different substituent group.Moreover, each substituent can be at any position on the respectivecyclopentadienyl or indenyl ring structure that conforms with the rulesof chemical valence. In an aspect, the number of substituents on Cp^(A)and/or on Cp^(B) and/or the positions of each substituent on Cp^(A)and/or on Cp^(B) are independent of each other. For instance, two ormore substituents on Cp^(A) can be different, or alternatively, eachsubstituent on Cp^(A) can be the same. Additionally or alternatively,two or more substituents on Cp^(B) can be different, or alternatively,all substituents on Cp^(B) can be the same. In another aspect, one ormore of the substituents on Cp^(A) can be different from the one or moreof the substituents on Cp^(B), or alternatively, all substituents onboth Cp^(A) and/or on Cp^(B) can be the same. In these and otheraspects, each substituent can be at any position on the respectivecyclopentadienyl or indenyl ring structure. If substituted, Cp^(A)and/or Cp^(B) independently can have one substituent, two substituents,three substituents, four substituents, and so forth.

In formula (I), each substituent on Cp^(A) and/or on Cp^(B)independently can be H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or aC₁ to C₃₆ hydrocarbylsilyl group. In some aspects, each substituentindependently can be H; alternatively, a halide; alternatively, a C₁ toC₁₈ hydrocarbyl group; alternatively, a C₁ to C₁₈ halogenatedhydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylsilyl group; alternatively, a C₁to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group; oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Thehalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, andC₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on Cp^(A)and/or on Cp^(B) in formula (I) can be any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (I)). Asubstituent on Cp^(A) and/or on Cp^(B) in formula (I) can be, in certainaspects, a C₁ to C₃₆ halogenated hydrocarbyl group, where thehalogenated hydrocarbyl group indicates the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thehydrocarbyl group. The halogenated hydrocarbyl group often can be ahalogenated alkyl group, a halogenated alkenyl group, a halogenatedcycloalkyl group, a halogenated aryl group, or a halogenated aralkylgroup. Representative and non-limiting halogenated hydrocarbyl groupsinclude pentafluorophenyl, trifluoromethyl (CF₃), and the like.

As a non-limiting example, if present, each substituent on Cp^(A) and/orCp^(B) independently can be H, Cl, CF₃, a methyl group, an ethyl group,a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, adecenyl group, a phenyl group, a tolyl group (or other substituted arylgroup), a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group; alternatively, H; alternatively, Cl;alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group; oralternatively, an allyldimethylsilyl group.

Illustrative and non-limiting examples of unbridged metallocenecompounds having formula (I) and/or suitable for use in the catalystcompositions of this invention can include the following compounds(Ph=phenyl):

and the like, as well as combinations thereof.

The metallocene compound is not limited solely to unbridged metallocenecompounds such as described above, or to suitable unbridged metallocenecompounds (e.g., with zirconium or hafnium) disclosed in U.S. Pat. Nos.7,199,073, 7,226,886, 7,312,283, and 7,619,047, which are incorporatedherein by reference in their entirety. For example, the metallocenecompound can comprise an unbridged zirconium and/or hafnium baseddinuclear metallocene compound. In one aspect, the metallocene compoundcan comprise an unbridged zirconium based homodinuclear metallocenecompound. In another aspect, the metallocene compound can comprise anunbridged hafnium based homodinuclear metallocene compound. In yetanother aspect, the metallocene compound can comprise an unbridgedzirconium and/or hafnium based heterodinuclear metallocene compound(i.e., a dinuclear compound with two hafniums, or two zirconiums, or onezirconium and one hafnium). The metallocene compound can compriseunbridged dinuclear metallocenes such as those described in U.S. Pat.Nos. 7,919,639 and 8,080,681, the disclosures of which are incorporatedherein by reference in their entirety. Illustrative and non-limitingexamples of dinuclear metallocene compounds suitable for use in catalystcompositions of this invention can include the following compounds:

and the like, as well as combinations thereof.

In some aspects of this invention, the metallocene compound can comprisea bridged metallocene compound. In one aspect, for instance, themetallocene compound can comprise a bridged zirconium or hafnium basedmetallocene compound. In another aspect, the metallocene compound cancomprise a bridged zirconium or hafnium based metallocene compound withan alkenyl substituent. In yet another aspect, the metallocene compoundcan comprise a bridged zirconium or hafnium based metallocene compoundwith an alkenyl substituent and a fluorenyl group. In still anotheraspect, the metallocene compound can comprise a bridged zirconium orhafnium based metallocene compound with a cyclopentadienyl group and afluorenyl group, and with an alkenyl substituent (e.g., a terminalalkenyl) on the bridging group and/or on the cyclopentadienyl group.

In some aspects, the metallocene compound can comprise a bridgedmetallocene compound having an aryl group substituent on the bridginggroup, while in other aspects, the metallocene compound can comprise adinuclear bridged metallocene compound with an alkenyl linking group.For example, the metallocene compound can comprise a bridged zirconiumor hafnium based metallocene compound with a fluorenyl group, and anaryl group on the bridging group; alternatively, a bridged zirconium orhafnium based metallocene compound with a cyclopentadienyl group andfluorenyl group, and an aryl group on the bridging group; alternatively,a bridged zirconium based metallocene compound with a fluorenyl group,and an aryl group on the bridging group; or alternatively, a bridgedhafnium based metallocene compound with a fluorenyl group, and an arylgroup on the bridging group. In these and other aspects, the aryl groupon the bridging group can be a phenyl group. Optionally, these bridgedmetallocenes can contain an alkenyl substituent (e.g., a terminalalkenyl) on the bridging group and/or on a cyclopentadienyl-type group.

In some aspects, the metallocene compound can comprise a bridgedzirconium or hafnium based metallocene compound with two indenyl groups(e.g., a bis-indenyl metallocene compound). Hence, the metallocenecompound can comprise a bridged zirconium based metallocene compoundwith two indenyl groups, or alternatively, a bridged hafnium basedmetallocene compound with two indenyl groups. In some aspects, an arylgroup can be present on the bridging group, while in other aspects,there are no aryl groups present on the bridging group. Optionally,these bridged indenyl metallocenes can contain an alkenyl substituent(e.g., a terminal alkenyl) on the bridging group and/or on the indenylgroup (one or both indenyl groups). The bridging atom of the bridginggroup can be, for instance, a carbon atom or a silicon atom;alternatively, the bridge can contain a chain of two carbon atoms, achain of two silicon atoms, and so forth.

The metallocene compound can comprise, in particular aspects of thisinvention, a bridged metallocene compound having formula (II):

Within formula (II), M, Cp, R^(X), R^(Y), E, and each X are independentelements of the bridged metallocene compound. Accordingly, the bridgedmetallocene compound having formula (II) can be described using anycombination of M, Cp, R^(X), R^(Y), E, and X disclosed herein.

The selections for M and each X in formula (II) are the same as thosedescribed herein above for formula (I). In formula (II), Cp can be asubstituted cyclopentadienyl, indenyl, or fluorenyl group. In oneaspect, Cp can be a substituted cyclopentadienyl group, while in anotheraspect, Cp can be a substituted indenyl group.

In some aspects, Cp can contain no additional substituents, e.g., otherthan bridging group E, discussed further herein below. In other aspects,Cp can be further substituted with one substituent, two substituents,three substituents, four substituents, and so forth. If present, eachsubstituent on Cp independently can be H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Importantly, each substituent on Cp can be either the same or adifferent substituent group. Moreover, each substituent can be at anyposition on the respective cyclopentadienyl, indenyl, or fluorenyl ringstructure that conforms with the rules of chemical valence. In general,any substituent on Cp, independently, can be H or any halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group described herein(e.g., as pertaining to substituents on Cp^(A) and Cp^(B) in formula(I)).

In one aspect, for example, each substituent on Cp independently can bea C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group. Inanother aspect, each substituent on Cp independently can be a C₁ to C₈alkyl group or a C₃ to C₈ alkenyl group. In yet another aspect, eachsubstituent on Cp^(C) independently can be H, Cl, CF₃, a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, adecenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthylgroup, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group.

Similarly, R^(X) and R^(Y) in formula (II) independently can be H or anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl groupdisclosed herein (e.g., as pertaining to substituents on Cp^(A) andCp^(B) in formula (I)). In one aspect, for example, R^(X) and R^(Y)independently can be H or a C₁ to C₁₂ hydrocarbyl group. In anotheraspect, R^(X) and R^(Y) independently can be a C₁ to C₁₀ hydrocarbylgroup. In yet another aspect, R^(X) and R^(Y) independently can be H,Cl, CF₃, a methyl group, an ethyl group, a propyl group, a butyl group(e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group, and the like. In still another aspect, R^(X)and R^(Y) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a phenylgroup, a tolyl group, or a benzyl group.

Bridging group E in formula (II) can be (i) a bridging group having theformula >E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A)and R^(B) independently can be H or a C₁ to C₁₈ hydrocarbyl group; (ii)a bridging group having the formula —CR^(C)R^(D)—CR^(E)R^(F)—, whereinR^(C), R^(D), R^(E), and R^(F) independently can be H or a C₁ to C₁₈hydrocarbyl group; or (iii) a bridging group having the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ can be C or Si, and R^(G),R^(H), R^(I), and R^(J) independently can be H or a C₁ to C₁₈hydrocarbyl group.

In the first option, the bridging group E can have the formula>E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A) and R^(B)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein. In some aspects of this invention, R^(A) and R^(B) independentlycan be a C₁ to C₁₂ hydrocarbyl group; alternatively, R^(A) and R^(B)independently can be a C₁ to C₈ hydrocarbyl group; alternatively, R^(A)and R^(B) independently can be a phenyl group, a C₁ to C₈ alkyl group,or a C₃ to C₈ alkenyl group; alternatively, R^(A) and R^(B)independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, acyclohexylphenyl group, a naphthyl group, a tolyl group, or a benzylgroup; or alternatively, R^(A) and R^(B) independently can be a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a phenyl group, or a benzyl group. In these and otheraspects, R^(A) and R^(B) can be either the same or different.

In the second option, the bridging group E can have the formula—CR^(C)R^(D)—CR^(E)R^(F)—, wherein R^(C), R^(D), R^(E), and R^(F)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein. For instance, R^(C), R^(D), R^(E), and R^(F) independently canbe H or a methyl group.

In the third option, the bridging group E can have the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ can be C or Si, and R^(G),R^(H), R^(I), and R^(J) independently can be H or any C₁ to C₁₈hydrocarbyl group disclosed herein. For instance, E⁵ can be Si, andR^(G), R^(H), R^(I), and R^(J) independently can be H or a methyl group.

Illustrative and non-limiting examples of bridged metallocene compoundshaving formula (II) and/or suitable for use in catalyst compositions ofthis invention can an include the following compounds (Me=methyl,Ph=phenyl; t-Bu=tert-butyl):

and the like, as well as combinations thereof.

Further examples of bridged metallocene compounds having formula (II)and/or suitable for use in catalyst compositions of this invention caninclude, but are not limited to, the following compounds:

and the like, as well as combinations thereof.

Suitable metallocene compounds are not limited solely to the bridgedmetallocene compounds such as described above. Other suitable bridgedmetallocene compounds (e.g., with zirconium or hafnium) are disclosed inU.S. Pat. Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939,and 7,619,047, which are incorporated herein by reference in theirentirety.

Ziegler-Natta Component

Catalyst compositions consistent with this invention can contain aZiegler-Natta component, typically a Ziegler-Natta component comprisingtitanium supported on MgCl₂. Generally, the amount of the MgCl₂ in theZiegler-Natta component is not particularly limited. However, the weightpercentage of magnesium (based on the weight of Ziegler-Natta component)often falls within a range from about 0.1 to about 10 wt. %. Forexample, the weight percentage can be in a range from about 0.5 to about10 wt. % magnesium, from about 1 to about 8 wt. % magnesium, or fromabout 1 to about 7 wt. % magnesium. In specific aspects, the weightpercentage of magnesium, based on the weight of the Ziegler-Nattacomponent, can be in a range from about 2 to about 9 wt. %, from about 3to about 8 wt. %, from about 3 to about 7 wt. %, from about 4 to about 7wt. %, or from about 4 to about 6 wt. % magnesium.

Likewise, the amount of titanium in the Ziegler-Natta component is notparticularly limited. The weight percentage of titanium (based on theweight of Ziegler-Natta component) typically falls within a range fromabout 0.1 to about 10 wt. %. For example, the weight percentage can bein a range from about 0.5 to about 10 wt. % titanium, from about 1 toabout 8 wt. % titanium, or from about 1 to about 7 wt. % titanium. Inspecific aspects, the weight percentage of titanium, based on the weightof the Ziegler-Natta component, can be in a range from about 2 to about9 wt. %, from about 3 to about 8 wt. %, from about 3 to about 7 wt. %,from about 4 to about 7 wt. %, or from about 4 to about 6 wt. %titanium.

Any suitable titanium compounds can be used in the processes forproducing a catalyst composition disclosed herein (or suitable titaniumcompounds present in the Ziegler-Natta component), such as titaniumhalides, titanium alkoxides, alkoxytitanium halides, and the like, aswell as combinations thereof. For instance, the titanium compound cancomprise, either singly or in combination, TiCl₃, TiCl₄, TiBr₄, TiI₄, orTiF₄.

In some aspects, the Ziegler-Natta component, in addition to containingtitanium supported on MgCl₂, can contain aluminum at any suitableamount. Additionally or alternatively, the Ziegler-Natta component canfurther comprise polyethylene at any suitable amount, for instance, theZiegler-Natta component can be a pre-polymerized Ziegler-Nattacomponent. Additionally or alternatively, the Ziegler-Natta componentcan be supported on an inert support, such as silica.

In other aspects, instead of titanium, the Ziegler-Natta component cancontain vanadium supported on MgCl₂, in an amount (in wt. %) similar tothat of titanium. Typical vanadium compounds that can be used in theprocesses for producing a catalyst composition disclosed herein caninclude vanadium halides, vanadium alkoxides, alkoxyvanadium halides,and the like, as well as combinations thereof.

Catalyst Compositions

Various processes for preparing a catalyst composition containing ametallocene compound, an activator-support, an organoaluminum compound,and a Ziegler-Natta component are disclosed and described herein. One ormore than one metallocene compound, activator-support, organoaluminumcompound, and Ziegler-Natta component can be employed in the disclosedprocesses and compositions. A process for producing a catalystcomposition consistent with aspects of this invention can comprise (orconsist essentially of, or consist of):

(a) contacting an activator-support and an organoaluminum compound for afirst period of time to form a precontacted mixture; and (b) contactingthe precontacted mixture with a metallocene compound and a Ziegler-Nattacomponent comprising titanium supported on MgCl₂ for a second period oftime to form the catalyst composition.

Generally, the features of any of the processes disclosed herein (e.g.,the activator-support, the organoaluminum compound, the metallocenecompound, the Ziegler-Natta component, the first period of time, and thesecond period of time, among others) are independently disclosed herein,and these features can be combined in any combination to furtherdescribe the disclosed processes. Suitable activator-supports,organoaluminum compounds, metallocene compounds, and Ziegler-Nattacomponents are discussed hereinabove. Moreover, other process steps canbe conducted before, during, and/or after any of the steps listed in thedisclosed processes, unless stated otherwise. Additionally, catalystcompositions produced in accordance with the disclosed processes arewithin the scope of this disclosure and are encompassed herein.

Step (a) of the process often can be referred to as the precontactingstep, and in the precontacting step, an activator-support can becombined with an organoaluminum compound for a first period of time toform a precontacted mixture. The precontacting step can be conducted ata variety of temperatures and time periods. For instance, theprecontacting step can be conducted at a precontacting temperature in arange from about 0° C. to about 100° C.; alternatively, from about 0° C.to about 75° C.; alternatively, from about 10° C. to about 75° C.;alternatively, from about 20° C. to about 60° C.; alternatively, fromabout 20° C. to about 50° C.; alternatively, from about 15° C. to about45° C.; or alternatively, from about 20° C. to about 40° C. In these andother aspects, these temperature ranges also are meant to encompasscircumstances where the precontacting step is conducted at a series ofdifferent temperatures, instead of at a single fixed temperature,falling within the respective ranges.

The duration of the precontacting step (the first period of time) is notlimited to any particular period of time. Hence, the first period oftime can be, for example, in a time period ranging from as little as1-10 seconds to as long as 48 hours, or more. The appropriate firstperiod of time can depend upon, for example, the precontactingtemperature, the amounts of the activator-support and the organoaluminumcompound in the precontacted mixture, the presence of diluents orsolvents in the precontacting step, and the degree of mixing, amongother variables. Generally, however, the first period of time can be atleast about 5 sec, at least about 10 sec, at least about 30 sec, atleast about 1 min, at least about 5 min, at least about 10 min, and soforth. Typical ranges for the first period of time can include, but arenot limited to, from about 1 sec to about 48 hr, from about 10 sec toabout 48 hr, from about 30 sec to about 24 hr, from about 30 sec toabout 6 hr, from about 1 min to about 12 hr, from about 5 min to about24 hr, or from about 10 min to about 8 hr, and the like.

Often, the precontacting step can be conducted by combining a slurry ofthe activator-support in a first diluent with a solution of theorganoaluminum compound in the same or a different diluent, and mixingto ensure sufficient contacting of the activator-support and theorganoaluminum compound. However, any suitable procedure known to thoseof skill in the art for thoroughly combining the activator-support andthe organoaluminum compound can be employed. Non-limiting examples ofsuitable hydrocarbon diluents can include, but are not limited to,propane, isobutane, n-butane, n-pentane, isopentane, neopentane,n-hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, benzene, toluene, xylene, ethylbenzene, and thelike, or combinations thereof. In another aspect, the activator-supportcan be present as a dry solid, and the precontacting step can beconducted by combining the dry activator-support with a solution of theorganoaluminum compound in a first diluent (e.g., a suitable hydrocarbonsolvent, such as cyclohexane, isobutane, n-butane, n-pentane,isopentane, neopentane, hexane, heptane, and the like, as well ascombinations thereof), and mixing to ensure sufficient contacting of theactivator-support and the organoaluminum compound. Accordingly, anysuitable procedure known to those of skill in the art for contacting orcombining the activator-support and the organoaluminum compound can beemployed.

In step (b) of the process, the precontacted mixture (often, a slurry)can be contacted with the metallocene compound and the Ziegler-Nattacomponent to form the catalyst composition. Step (b), likewise, can beconducted at a variety of temperatures and time periods. For instance,step (b) can be conducted at a temperature in a range from about 0° C.to about 100° C.; alternatively, from about 10° C. to about 75° C.;alternatively, from about 20° C. to about 60° C.; alternatively, fromabout 15° C. to about 45° C.; or alternatively, from about 20° C. toabout 40° C. In these and other aspects, these temperature ranges arealso meant to encompass circumstances where step (b) is conducted at aseries of different temperatures, instead of at a single fixedtemperature, falling within the respective ranges. As an example, theprecontacted mixture, the metallocene compound, and the Ziegler-Nattacomponent can be contacted at an elevated temperature, following bycooling to a lower temperature for longer term storage of the finishedcatalyst composition.

The second period of time is not limited to any particular period oftime. Hence, the second period of time can range from as little as 1-10seconds to as long as 48 hours, or more. The appropriate second periodof time can depend upon, for example, the temperature, the amounts ofthe precontacted mixture and the metallocene and Ziegler-Nattacomponents, the presence of diluents or solvents in step (b), the degreeof mixing, and considerations for long term storage, among othervariables. Generally, however, the second period of time can be at leastabout 5 sec, at least about 10 sec, at least about 30 sec, at leastabout 1 min, at least about 5 min, at least about 10 min, and so forth.Assuming the catalyst composition is not intended for long term storage,which could extend for days or weeks, typical ranges for the secondperiod of time can include, but are not limited to, from about 1 sec toabout 48 hr, from about 10 sec to about 48 hr, from about 30 sec toabout 24 hr, from about 30 sec to about 6 hr, from about 1 min to about6 hr, from about 5 min to about 24 hr, or from about 10 min to about 8hr.

In related aspects, a catalyst composition consistent with thisinvention can comprise (A) a precontacted mixture comprising anactivator-support and an organoaluminum compound, (B) a metallocenecompound, and (C) a Ziegler-Natta component comprising titaniumsupported on MgCl₂.

In another aspect, and unexpectedly, the activity of the catalystcomposition can be greater (e.g., by at least about 2%, by at leastabout 10%, by at least about 25%, by at least about 100%, from about 1%to about 100%, from about 2% to about 50%, from about 5% to about 50%,from about 15% to about 1000%, or from about 25% to about 800% greater)than that of a catalyst system obtained by first combining theactivator-support and the metallocene compound, and then combining theorganoaluminum compound and the Ziegler-Natta component, under the samepolymerization conditions. The same polymerization conditions refer toslurry polymerization conditions, using isobutane as a diluent, and witha polymerization temperature of 80° C. and a reactor pressure of 260psig. Moreover, all components used to prepare the catalyst systems areheld constant (e.g., same amount/type of metallocene compound, sameamount/type of Ziegler-Natta component, same amount/type oforganoaluminum, same amount/type of activator-support, such as fluoridedsilica-coated alumina or sulfated alumina) and all polymerizationconditions are held constant (e.g., same polymerization temperature,same pressure). Hence, the only difference is the order or sequence ofcontacting the respective catalyst components (precontacting theactivator-support and the organoaluminum compound versus noprecontacting).

In other aspects of this invention, a process for preparing a catalystcomposition containing a metallocene compound, a Ziegler-Nattacomponent, an activator-support, and an organoaluminum compound cancomprise (or consist essentially of, or consist of) contacting, in anyorder:

(i) a metallocene compound;

(ii) a Ziegler-Natta component comprising titanium supported on MgCl₂;

(iii) an activator-support; and

(iv) an organoaluminum compound; to form the catalyst composition.

Generally, the features of this process (e.g., the activator-support,the organoaluminum compound, the metallocene compound, the Ziegler-Nattacomponent, and the order of contacting, among others) are independentlydescribed herein, and these features can be combined in any combinationto further describe the disclosed processes. Moreover, other processsteps can be conducted before, during, and/or after any of the stepslisted in the disclosed processes, unless stated otherwise.Additionally, catalyst compositions produced in accordance with thisprocess are within the scope of this disclosure and are encompassedherein.

In this process, the various components can be contacted or combined inany order, and under any suitable conditions, to form the catalystcomposition. Thus, a variety of temperatures and time periods can beemployed. For instance, the catalyst components can be contacted atemperature in a range from about 0° C. to about 100° C.; alternatively,from about 0° C. to about 75° C.; alternatively, from about 10° C. toabout 75° C.; alternatively, from about 20° C. to about 60° C.;alternatively, from about 20° C. to about 50° C.; alternatively, fromabout 15° C. to about 45° C.; or alternatively, from about 20° C. toabout 40° C. In these and other aspects, these temperature ranges alsoare meant to encompass circumstances where the components are contactedat a series of different temperatures, instead of at a single fixedtemperature, falling within the respective ranges. As an example, theinitial contacting of the components of the catalyst system can beconducted at an elevated temperature, following by cooling to a lowertemperature for longer term storage of the finished catalystcomposition.

The duration of the contacting of the components to form the catalystcomposition is not limited to any particular period of time. Hence, thisperiod of time can be, for example, from as little as 1-10 seconds to aslong as 24-48 hours, or more. The appropriate period of time can dependupon, for example, the contacting temperature, the respective amounts ofthe activator-support, metallocene compound, Ziegler-Natta component,and organoaluminum compound to be contacted or combined, the degree ofmixing, and considerations for long term storage, among other variables.Generally, however, the period of time for contacting can be at leastabout 5 sec, at least about 10 sec, at least about 30 sec, at leastabout 1 min, at least about 5 min, at least about 10 min, and so forth.Assuming the catalyst composition is not intended for long term storage,which could extend for days or weeks, typical ranges for the contactingtime can include, but are not limited to, from about 1 sec to about 48hr, from about 10 sec to about 48 hr, from about 30 sec to about 24 hr,from about 30 sec to about 6 hr, from about 1 min to about 6 hr, fromabout 5 min to about 24 hr, or from about 10 min to about 8 hr, and thelike.

Often, the metallocene compound can be present as a solution in anysuitable non-polar hydrocarbon, non-limiting examples of which caninclude, but are not limited to, propane, isobutane, n-butane,n-pentane, isopentane, neopentane, n-hexane, heptane, octane,cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane,benzene, toluene, xylene, ethylbenzene, and the like, as well ascombinations thereof. Often, the activator-support can be present as aslurry, and the diluent can be the same as or different from thenon-polar hydrocarbon used for the metallocene solution.

In related aspects, a catalyst composition consistent with thisinvention can comprise (i) a metallocene compound, (ii) a Ziegler-Nattacomponent comprising titanium supported on MgCl₂, (iii) anactivator-support, and (iv) an organoaluminum compound.

Generally, in the catalyst compositions and methods of their preparationdisclosed herein, the weight ratio of activator-support(s) toorganoaluminum compound(s) can be in a range from about 1:10 to about1000:1, or from about 1:5 to about 1000:1. If more than oneorganoaluminum compound and/or more than one activator-support areemployed, this ratio is based on the total weight of each respectivecomponent. In another aspect, the weight ratio of the activator-supportto the organoaluminum compound can be in a range from about 1:1 to about500:1, from about 1:3 to about 200:1, or from about 1:1 to about 100:1.

Likewise, the weight ratio of metallocene compound(s) toactivator-support(s) can be in a range from about 1:1 to about1:1,000,000, or from about 1:5 to about 1:250,000. If more than onemetallocene compound and/or more than one activator-support areemployed, this ratio is based on the total weight of each respectivecomponent. In another aspect, the weight ratio of metallocene compoundto activator-support can be in a range from about 1:10 to about1:10,000, or from about 1:20 to about 1:1000.

The catalyst composition, in certain aspects of this invention, issubstantially free of aluminoxanes, organoboron or organoboratecompounds, ionizing ionic compounds, and/or other similar materials;alternatively, substantially free of aluminoxanes; alternatively,substantially free or organoboron or organoborate compounds; oralternatively, substantially free of ionizing ionic compounds. In theseaspects, the catalyst composition has catalyst activity in the absenceof these additional materials. For example, a catalyst compositionconsistent with aspects of the present invention can consist essentiallyof (i) a metallocene compound, (ii) a Ziegler-Natta component comprisingtitanium supported on MgCl₂, (iii) an activator-support, and (iv) anorganoaluminum compound, wherein no other materials are present in thecatalyst composition which would increase/decrease the activity of thecatalyst composition by more than about 10% from the catalyst activityof the catalyst composition in the absence of said materials.

The molar ratio of the metallocene component to the Ziegler-Nattacomponent in the catalyst composition is not limited to any particularrange. However, in some aspects, the molar ratio of the metallocenecompound (e.g., Zr or Hf) to Ti (in the Ziegler-Natta component) in thecatalyst composition can be in a range from about 10:1 to about 1:10,from about 8:1 to about 1:8, from about 5:1 to about 1:5, from about 4:1to about 1:4, from about 3:1 to about 1:3, from about 3:1 to about 1:5,from about 2.8:1 to about 1:2.5, from about 2:1 to about 1:2, from about1.5:1 to about 1:1.5, from about 1.25:1 to about 1:1.25, or from about1.1:1 to about 1:1.1. If more than one metallocene compound and/or morethan one Ziegler-Natta component are employed, this ratio is based onthe total moles of the respective components.

Catalyst compositions of the present invention can have unexpectedlyhigh catalyst activity. Generally, the catalyst compositions have acatalyst activity greater than about 500 grams of ethylene polymer(homopolymer, copolymer, etc., as the context requires) per gram of theactivator-support per hour (abbreviated g/g/hr). In another aspect, thecatalyst activity can be greater than about 1,000, greater than about1,500, or greater than about 2,000 g/g/hr. In still another aspect,catalyst compositions of this invention can be characterized by having acatalyst activity greater than about 2,500, greater than about 3,000, orgreater than about 4,000 g/g/hr, and often can range up to 5,000-10,000g/g/hr. These activities are measured under slurry polymerizationconditions, with a triisobutylaluminum co-catalyst, using isobutane asthe diluent, at a polymerization temperature of 80° C. and a reactorpressure of about 260 psig.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof; alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise any of the catalyst compositionsdescribed herein, and/or the catalyst composition can be produced by anyof the processes for preparing catalyst compositions described herein.For instance, the catalyst composition can comprise (A) a precontactedmixture comprising an activator-support and an organoaluminum compound,(B) a metallocene compound, and (C) a Ziegler-Natta component comprisingtitanium supported on MgCl₂, or the catalyst composition can comprise(i) a metallocene compound, (ii) a Ziegler-Natta component comprisingtitanium supported on MgCl₂, (iii) an activator-support, and (iv) anorganoaluminum compound. The components of the catalyst compositions aredescribed herein.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include, but are not limited to, those that can be referredto as a batch reactor, slurry reactor, gas-phase reactor, solutionreactor, high pressure reactor, tubular reactor, autoclave reactor, andthe like, or combinations thereof. Suitable polymerization conditionsare used for the various reactor types. Gas phase reactors can comprisefluidized bed reactors or staged horizontal reactors. Slurry reactorscan comprise vertical or horizontal loops. High pressure reactors cancomprise autoclave or tubular reactors. Reactor types can include batchor continuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed into a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and8,822,608, each of which is incorporated herein by reference in itsentirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. Representative gasphase reactors are disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790,5,436,304, 7,531,606, and 7,598,327, each of which is incorporated byreference in its entirety herein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages to the polymerizationreaction process.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and an optional olefin comonomer under polymerization conditionsto produce an olefin polymer. The olefin polymer (e.g., an ethylenehomopolymer or copolymer) produced by the process can have any of thepolymer properties disclosed herein, for example, a melt index of lessthan or equal to about 15 g/10 min, and/or a high load melt index ofless than or equal to about 150 g/10 min, and/or a ratio of Mw/Mn in arange from about 2.5 to about 15, and/or a density in a range from about0.89 g/cm³ to about 0.96 g/cm³, and/or low levels of long chain branches(LCB), and/or a decreasing or substantially constant short chain branchdistribution (SCBD), and/or any of the characteristics from ATREF thatare described herein, e.g., from about 0.5 to about 4 wt. % of thepolymer eluted below a temperature of 40° C., from about 40 to about 62wt. % of the polymer eluted between 40 and 76° C., from about 2 to about21 wt. % of the polymer eluted between 76 and 86° C., and from about 29to about 40 wt. % of the polymer eluted above a temperature of 86° C.;or from about 1 to about 18 wt. % (or from about 1 to about 16 wt. %) ofthe polymer eluted below a temperature of 40° C., from about 1 to about15 wt. % (or from about 1 to about 10 wt. %) of the polymer elutedbetween 76 and 86° C., from about 27 to about 60 wt. % (or from about 29to about 60 wt. %) of the polymer eluted above a temperature of 86° C.,and the remainder of the polymer (to reach 100 wt. %) eluted between 40and 76° C.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition (i.e., any catalyst composition disclosed herein)with an olefin monomer and optionally an olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer, wherein the polymerization process is conducted inthe absence of added hydrogen (no hydrogen is added to thepolymerization reactor system). As one of ordinary skill in the artwould recognize, hydrogen can be generated in-situ by catalystcompositions in various olefin polymerization processes, and the amountgenerated can vary depending upon the specific catalyst componentsemployed, the type of polymerization process used, the polymerizationreaction conditions utilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition (i.e., any catalystcomposition disclosed herein) with an olefin monomer and optionally anolefin comonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the polymerizationprocess is conducted in the presence of added hydrogen (hydrogen isadded to the polymerization reactor system). For example, the ratio ofhydrogen to the olefin monomer in the polymerization process can becontrolled, often by the feed ratio of hydrogen to the olefin monomerentering the reactor. The added hydrogen to olefin monomer ratio in theprocess can be controlled at a weight ratio which falls within a rangefrom about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, orfrom about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymers (e.g.,ethylene homopolymers and ethylene/α-olefin copolymers) produced by anyof the polymerization processes disclosed herein. Articles ofmanufacture can be formed from, and/or can comprise, the polymersproduced in accordance with this invention.

Polymers and Articles

Generally, olefin polymers encompassed herein can include any polymerproduced from any olefin monomer and comonomer(s) described herein. Forexample, the olefin polymer can comprise an ethylene homopolymer, apropylene homopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

An illustrative and non-limiting example of an olefin polymer (e.g., anethylene copolymer) of the present invention can have a melt index ofless than or equal to about 15 g/10 min, a ratio of Mw/Mn in a rangefrom about 2 to about 15, and a density in a range from about 0.89 g/cm³to about 0.96 g/cm³. Another illustrative and non-limiting example of anolefin polymer (e.g., an ethylene copolymer) of the present inventioncan have a high load melt index of less than or equal to about 150 g/10min, a ratio of Mw/Mn in a range from about 2.5 to about 15, and adensity in a range from about 0.89 g/cm³ to about 0.96 g/cm³. Thesepolymers, in further aspects, can be characterized by low levels of longchain branches (LCB), and/or by a decreasing or substantially constantshort chain branch distribution (SCBD). In some aspects, the polymer canbe characterized by less than about 4 wt. % of the polymer eluted belowa temperature of 40° C. in an ATREF test, and/or by from about 40 toabout 62 wt. % of the polymer eluted between 40 and 76° C. in an ATREFtest, and/or by from about 2 to about 21 wt. % of the polymer elutedbetween 76 and 86° C. in an ATREF test, and/or by from about 29 to about40 wt. % of the polymer eluted above a temperature of 86° C. in an ATREFtest. In other aspects, the polymer can be characterized, in an ATREFtest, by from about 1 to about 18 wt. % (or from about 1 to about 16 wt.%) of the polymer eluted below a temperature of 40° C., by from about 1to about 15 wt. % (or from about 1 to about 10 wt. %) of the polymereluted between 76 and 86° C., by from about 27 to about 60 wt. % (orfrom about 29 to about 60 wt. %) of the polymer eluted above atemperature of 86° C., and the remainder of the polymer (to reach 100wt. %) eluted between 40 and 76° C. These illustrative and non-limitingexamples of olefin polymers consistent with the present invention alsocan have any of the polymer properties listed below and in anycombination.

Polymers of ethylene (homopolymers, copolymers, etc.) produced inaccordance with some aspects of this invention generally can have a meltindex (MI) from 0 to about 15 g/10 min. Melt indices in the range from 0to about 12, from 0 to about 10, from 0 to about 8, or from 0 to about 5g/10 min, are contemplated in other aspects of this invention. Forexample, a polymer of the present invention can have a MI in a rangefrom 0 to about 2, from about 0.1 to about 2, from about 0.1 to about1.5, from about 0.2 to about 1.5, or from about 0.5 to about 1.5 g/10min.

Consistent with certain aspects of this invention, ethylene polymersdescribed herein can have a high load melt index (HLMI) in a range from0 to about 150, from 0 to about 100, from 0 to about 75, or from 0 toabout 50 g/10 min. In further aspects, ethylene polymers describedherein can have a HLMI in a range from 0 to about 40, from 0 to about20, from about 2 to about 40, from about 3 to about 35, from about 4 toabout 30, or from about 5 to about 25 g/10 min.

The densities of ethylene-based polymers (e.g., ethylene homopolymers,ethylene copolymers) produced using the catalyst systems and processesdisclosed herein often are less than or equal to about 0.965 g/cm³, forexample, less than or equal to about 0.96 g/cm³, and often can rangedown to about 0.88 g/cm³. Yet, in particular aspects, the density can bein a range from about 0.89 to about 0.96, such as, for example, fromabout 0.90 to about 0.96, from about 0.90 to about 0.95, from about 0.90to about 0.935, from about 0.91 to about 0.96, from about 0.91 to about0.95, from about 0.91 to about 0.93, from about 0.91 to about 0.925, orfrom about 0.915 to about 0.945 g/cm³.

Generally, polymers produced in aspects of the present invention areessentially linear or have very low levels of long chain branching, withtypically less than about 0.01 long chain branches (LCB) per 1000 totalcarbon atoms, and similar in LCB content to polymers shown, for example,in U.S. Pat. Nos. 7,517,939, 8,114,946, and 8,383,754, which areincorporated herein by reference in their entirety. In other aspects,the number of LCB per 1000 total carbon atoms can be less than about0.008, less than about 0.007, less than about 0.005, or less than about0.003 LCB per 1000 total carbon atoms.

In an aspect, ethylene polymers described herein can have a ratio ofMw/Mn, or the polydispersity index, in a range from about 2 to about 15,from about 2.5 to about 15, from about 3 to about 15, from about 3 toabout 12, or from about 3 to about 8. In another aspect, ethylenepolymers described herein can have a Mw/Mn in a range from about 2.5 toabout 12, from about 2.5 to about 8, from about 2.5 to about 7, fromabout 4 to about 10, or from about 4 to about 8.

In an aspect, ethylene polymers described herein can have a ratio ofMz/Mw in a range from about 1.8 to about 12, from about 1.8 to about 10,from about 2 to about 12, or from about 2 to about 10. In anotheraspect, ethylene polymers described herein can have a Mz/Mw in a rangefrom about 2 to about 8, from about 2 to about 6, from about 2 to about5, from about 3 to about 8, or from about 3 to about 6.

In an aspect, ethylene polymers described herein can have aweight-average molecular weight (Mw) in a range from about 20,000 toabout 600,000, from about 30,000 to about 500,000, from about 40,000 toabout 400,000, from about 100,000 to about 300,000, or from about120,000 to about 260,000 g/mol. In another aspect, ethylene polymersdescribed herein can have a number-average molecular weight (Mn) in arange from about 5,000 to about 100,000, from about 6,000 to about80,000, from about 20,000 to about 75,000, or from about 20,000 to about50,000 g/mol. In yet another aspect, ethylene polymers described hereincan have a z-average molecular weight (Mz) in a range from about 50,000to about 4,000,000, from about 100,000 to about 3,500,000, from about200,000 to about 3,000,000, from about 200,000 to about 1,200,000, orfrom about 300,000 to about 1,000,000 g/mol.

Ethylene polymers consistent with certain aspects of the invention oftencan have a bimodal molecular weight distribution (as determined usinggel permeation chromatography (GPC) or other suitable analyticaltechnique). Typically, a bimodal molecular weight distribution can becharacterized as having an identifiable high molecular weight component(or distribution) and an identifiable low molecular weight component (ordistribution).

In one aspect of this invention, ethylene copolymers, for example,produced using the polymerization processes and catalyst systemsdescribed herein can have a generally decreasing SCBD (the number ofshort chain branches per 1000 total carbon atoms at Mz is less than atMn), while in another aspect, the ethylene copolymers can have asubstantially constant SCBD (as described in U.S. Pat. No. 9,217,049,incorporated herein by reference in its entirety).

In particular aspects of this invention, the olefin polymers describedherein can be a reactor product (e.g., a single reactor product), forexample, not a post-reactor blend of two polymers, for instance, havingdifferent molecular weight characteristics. As one of skill in the artwould readily recognize, physical blends of two different polymer resinscan be made, but this necessitates additional processing and complexitynot required for a reactor product.

Ethylene copolymers consistent with aspects of this invention can becharacterized according to the polymer fractions eluted using ATREF. Onesuch polymer can have from about 0.5 to about 4 wt. % of the polymereluted below a temperature of 40° C. (in the ATREF test), and from about29 to about 40 wt. % of the polymer eluted above a temperature of 86° C.In another aspect, the polymer can be characterized by from about 0.5 toabout 4 wt. % of the polymer eluted below a temperature of 40° C., fromabout 40 to about 62 wt. % of the polymer eluted between 40 and 76° C.,from about 2 to about 21 wt. % of the polymer eluted between 76 and 86°C., and from about 29 to about 40 wt. % of the polymer eluted above atemperature of 86° C. As one of skill in the art would readilyrecognize, the total of these weight percentages does not exceed 100 wt.%.

In particular aspects of this invention, the ethylene copolymers can becharacterized by the following polymer fractions eluted using ATREF:from about 1 to about 18 wt. % (or from about 1 to about 16 wt. %, orfrom about 1 to about 8 wt. %) of the polymer eluted below a temperatureof 40° C.; from about 1 to about 15 wt. % (or from about 1 to about 10wt. %, or from about 1 to about 8 wt. %) of the polymer eluted between76 and 86° C.; from about 27 to about 60 wt. % (or from about 29 toabout 60 wt. %, or from about 28 to about 48 wt. %, or from about 29 toabout 40 wt. %) of the polymer eluted above a temperature of 86° C.; andthe remaining percentage of the polymer (to reach 100 wt. %) elutedbetween 40 and 76° C.

Olefin polymers, whether homopolymers, copolymers, and so forth, can beformed into various articles of manufacture. Articles which can comprisepolymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a container forchemicals, a drum, a fiber or fabric, a food packaging film orcontainer, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, an outdoor storage product, outdoor play equipment, a pipe, asheet or tape, a toy, or a traffic barrier, and the like. Variousprocesses can be employed to form these articles. Non-limiting examplesof these processes include injection molding, blow molding, rotationalmolding, film extrusion, sheet extrusion, profile extrusion,thermoforming, and the like. Additionally, additives and modifiers areoften added to these polymers in order to provide beneficial polymerprocessing or end-use product attributes. Such processes and materialsare described in Modern Plastics Encyclopedia, Mid-November 1995 Issue,Vol. 72, No. 12; and Film Extrusion Manual—Process, Materials,Properties, TAPPI Press, 1992; the disclosures of which are incorporatedherein by reference in their entirety. In some aspects of thisinvention, an article of manufacture can comprise any of ethylenecopolymers described herein, and the article of manufacture can be afilm product or a molded product.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise (i) a metallocene compound, (ii) aZiegler-Natta component comprising titanium supported on MgCl₂, (iii) anactivator-support, and (iv) an organoaluminum compound; and (ii) formingan article of manufacture comprising the olefin polymer. The formingstep can comprise blending, melt processing, extruding, molding, orthermoforming, and the like, including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, modifications, and equivalentsthereof which, after reading the description herein, may suggestthemselves to one of ordinary skill in the art without departing fromthe spirit of the present invention or the scope of the appended claims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight. Polymer density was determined in grams per cubiccentimeter (g/cm³) on a compression molded sample, cooled at about 15°C. per hour, and conditioned for about 40 hours at room temperature inaccordance with ASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, MA) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 400 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mnis the number-average molecular weight, Mw is the weight-averagemolecular weight, and Mz is the z-average molecular weight.

The long chain branches (LCB) per 1000 total carbon atoms can becalculated using the method of Janzen and Colby (J. Mol. Struct.,485/486, 569-584 (1999)), from values of zero shear viscosity, η_(o)(determined from the Carreau-Yasuda model), and measured values of Mwobtained using a Dawn EOS multiangle light scattering detector (Wyatt).See also U.S. Pat. No. 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y.Yu, D. C. Rohlfing, G. R Hawley, and P. J. DesLauriers, PolymerPreprint, 44, 50, (2003). These references are incorporated herein byreference in their entirety.

The ATREF procedure was as follows. Forty mg of the polymer sample and20 mL of 1,2,4-trichlorobenzene (TCB) were sequentially charged into avessel on a PolyChar TREF 200+instrument. After dissolving the polymer,an aliquot (500 microliters) of the polymer solution was loaded on thecolumn (stainless steel shots) at 150° C. and cooled at 0.5° C./min to35° C. Then, the elution was begun with a 0.5 mL/min TCB flow rate andheating at 1° C./min up to 120° C., and analyzing with an IR detector.

Short chain branch (SCB) content and short chain branching distribution(SCBD) across the molecular weight distribution can be determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system is a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, MA) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IR5) (Polymer Char, Spain) canbe connected to the GPC columns via a hot-transfer line. Chromatographicdata is obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions are set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell are set at 150° C., while the temperature ofthe electronics of the IR5 detector is set at 60° C. Short chainbranching content can be determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve is a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) are used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution can beobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume isconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on aRheometrics Scientific, Inc. ARES rheometer using parallel-plategeometry. All rheological tests were performed at 190° C. The complexviscosity |η*| versus frequency (ω) data were then curve fitted usingthe modified three parameter Carreau-Yasuda (CY) empirical model toobtain the zero shear viscosity—η₀, characteristic viscous relaxationtime—τ_(η), and the breadth parameter—a. The simplified Carreau-Yasuda(CY) empirical model is as follows.

${\left| {\eta^{*}(\omega)} \right| = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}\text{/}a}}},$wherein: |η*(ω)|=magnitude of complex shear viscosity;

-   -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   a=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters may be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

Fluorided silica-coated alumina activator-supports were prepared asfollows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g, apore volume of about 1.3 mL/g, and an average particle size of about 100microns. The alumina was first calcined in dry air at about 600° C. forapproximately 6 hours, cooled to ambient temperature, and then contactedwith tetraethylorthosilicate in isopropanol to equal 25 wt. % SiO₂.After drying, the silica-coated alumina was calcined at 600° C. for 3hours. Fluorided silica-coated alumina (7 wt. % F) was prepared byimpregnating the calcined silica-coated alumina with an ammoniumbifluoride solution in methanol, drying, and then calcining for 3 hoursat 600° C. in dry air. Afterward, the fluorided silica-coated alumina(FSCA) was collected and stored under dry nitrogen, and was used withoutexposure to the atmosphere.

Sulfated alumina activator-supports were prepared as follows. As above,bohemite was obtained from W.R. Grace & Company under the designation“Alumina A.” This material was impregnated to incipient wetness with anaqueous solution of ammonium sulfate to equal about 15% sulfate. Thismixture was then placed in a flat pan and allowed to dry under vacuum atapproximately 110° C. for about 16 hours. To calcine the resultantpowdered mixture, the material was fluidized in a stream of dry air atabout 550° C. for about 6 hours. Afterward, the sulfated alumina (SA)was collected and stored under dry nitrogen, and was used withoutexposure to the atmosphere.

Two different Ziegler-Natta components were evaluated. The firstZiegler-Natta component (“K”) contained about 14-19 wt. % titaniumcompounds (TiCl₃/TiCl₄), about 17-24 wt. % MgCl₂, about 9-13 wt. %aluminum compounds, about 43-53 wt. % polyethylene, and less than about3 wt. % heptane. The overall metal concentration for Ti was in the3.5-5.9 wt. % range, and for Mg was in the 4.1-5.8 wt. % range. Thesecond Ziegler-Natta component (“B”) contained titanium compounds(TiCl₃/TiCl₄), MgCl₂, and aluminum compounds totaling about 85-99 wt. %,and less than 15 wt. % of hexane.

The structures for metallocenes MET 1, MET 2, MET 3, and MET 4 are shownbelow:

Examples 1-47

Examples 1-43 and 45-47 were produced using the following polymerizationprocedure. The polymerization runs were conducted in a one-gallonstainless steel reactor, and isobutane (2 L) was used in all runs.Metallocene solutions were prepared at about 1 mg/mL in toluene. Underan isobutane purge, the organoaluminum compound (1 mmol, TIBA, 25% inheptanes), the activator-support (FSCA or SA), the metallocene solution,and the Ziegler-Natta component were added in that order through acharge port while slowly venting isobutane vapor. The charge port wasclosed and isobutane was added. The contents of the reactor were stirredand heated to the desired run temperature of about 80° C., and ethyleneand 1-hexene (if used, ranging from 20 to 150 grams) were thenintroduced into the reactor. Hydrogen (if used, ranging from 30 to 500mg) was added from a 325 cc auxiliary vessel. Ethylene was fed on demandto maintain the target pressure of 260 psig pressure for the 30 minutelength of the polymerization run. The reactor was maintained at thedesired temperature throughout the run by an automated heating-coolingsystem. After venting of the reactor, purging, and cooling, theresulting polymer product was dried under reduced pressure.

Table I summarizes certain information relating to the polymerizationexperiments of Examples 1-43 using dual catalyst systems containing ametallocene compound (MET 1, MET 2, MET 3, or MET 4) and a Ziegler-Nattacomponent (B or K). Weights of the activator-support, metallocenecompound, and Ziegler-Natta (ZN) component are shown in Table I,however, the molar ratios of Zr:Ti ranged from about 0.2:1 to 2.6:1, andthe molar ratios of Hf:Ti ranged from about 0.7:1 to 2.5:1, in Examples1-43. The weight of polymer produced and the corresponding catalystactivity (in grams of polymer per gram of activator-support per hour,g/g/hr) also are listed in Table I. Catalyst activities weresurprisingly high, and ranged from over 700 to almost 8000 g/g/hr. Theseresults are unexpected because it can be difficult to combine aZiegler-Natta component and a metallocene compound together in onereactor and efficiently produce polyethylene, due to the differencesbetween these two types of catalytic materials. Often, there ispoisoning between the Ziegler-Natta component and the metallocenecompound, resulting in the loss of the polymerization activities.However, as shown in Table I, highly active dual catalyst systems wereproduced, and in some cases, the overall catalyst activity was similarto the sum of the individual contributions from the Ziegler-Nattacomponent and from the metallocene compound.

Table II summarizes the molecular weight characterization of thepolymers of Examples 1-43, as well as the polymer density (g/cc), meltindex (MI, g/10 min), high load melt index (HLMI, g/10 min), and zeroshear viscosity (η₀, units of Pa·s). Table II demonstrates that polymershaving a wide range of molecular weights and densities were producedwith different metallocene compounds and different Ziegler-Nattacomponents. Polymer densities ranged from over 0.89 to almost 0.96 g/cc,and ratios of Mw/Mn ranged from about 2.6 to 12.4.

FIG. 1 illustrates the molecular weight distributions (amount of polymerversus molecular weight) for the polymers of Examples 1-2 and 8, FIG. 2illustrates the molecular weight distributions of the polymers ofExamples 10, 12, and 17, FIG. 3 illustrates the molecular weightdistributions of the polymers of Examples 19-20 and 26, FIG. 4illustrates the molecular weight distributions of the polymers ofExamples 33-34 and 39, and FIG. 5 illustrates the molecular weightdistributions of the polymers of Examples 40-41 and 43. Portions of theoverall polymer produced from the Ziegler-Natta component and from themetallocene compound were evident in many of Examples 1-43.

Although not tested, it was expected that the polymers of Examples 1-43would have low levels of long chain branches (LCB), with typically lessthan 0.008 LCB, and more likely less than 0.005 LCB, per 1000 totalcarbon atoms. Additionally, although not tested, it was expected thatthe polymers of Examples 1-43 would have decreasing or substantiallyflat short chain branching distributions.

FIG. 6 illustrates the ATREF profiles of the polymers of Examples 7, 10,and 44. Example 44 was a comparative polymer produced in a dual reactorsystem containing a solution reactor. For the ATREF analysis of Example7, 3 wt. % of the polymer was eluted below a temperature of 40° C., 58wt. % of the polymer was eluted between 40° C. and 76° C., 3 wt. % waseluted between 76° C. and 86° C., and 36 wt. % was eluted above atemperature of 86° C. For Example 10, 1 wt. % was eluted below atemperature of 40° C., 69 wt. % was eluted between 40° C. and 90° C.,and 30 wt. % was eluted above a temperature of 90° C. For Example 44, 1wt. % was eluted below a temperature of 40° C., 51 wt. % was elutedbetween 40° C. and 77° C., 21 wt. % was eluted between 77° C. and 86°C., and 27 wt. % was eluted above a temperature of 86° C.

Table III summarizes certain information relating to the polymerizationexperiments of Examples 45-47 using dual catalyst systems containing ametallocene compound (MET 1) and a Ziegler-Natta component (K). In theseexamples, 35-60 grams of 1-hexene were used. Weights of theactivator-support (sulfated alumina, SA), metallocene compound, andZiegler-Natta (ZN) component are shown in Table III; the molar ratios ofZr:Ti ranged from about 0.2:1 to 2.6:1. The weight of polymer producedand the corresponding catalyst activity (in grams of polymer per gram ofactivator-support per hour, g/g/hr) also are listed in Table III.Catalyst activities were surprisingly high, and ranged from over 3500 toalmost 4000 g/g/hr.

Table IV summarizes the molecular weight characterization of thepolymers of Examples 45-47, as well as the polymer density (g/cc), meltindex (MI, g/10 min), high load melt index (HLMI, g/10 min), and zeroshear viscosity (η₀, units of Pa·s). Table IV demonstrates polymershaving densities in the 0.915-0.925 range, melt indices less than 1, andHLMI's in the 14-18 range. Although not tested, it was expected that thepolymers of Examples 45-47 would have low levels of long chain branches(LCB), with typically less than 0.008 LCB, and more likely less than0.005 LCB, per 1000 total carbon atoms. Additionally, although nottested, it was expected that the polymers of Examples 45-47 would have adecreasing short chain branching distribution.

FIGS. 7-9 illustrate the ATREF profiles of the polymers of Examples45-47, respectively. For the ATREF analysis of Example 45, 3 wt. % ofthe polymer was eluted below a temperature of 40° C., 55 wt. % of thepolymer was eluted between 40° C. and 76° C., 6 wt. % was eluted between76° C. and 86° C., and 36 wt. % was eluted above a temperature of 86° C.For the ATREF analysis of Example 46, 4 wt. % of the polymer was elutedbelow a temperature of 40° C., 60 wt. % of the polymer was elutedbetween 40° C. and 76° C., 7 wt. % was eluted between 76° C. and 86° C.,and 29 wt. % was eluted above a temperature of 86° C. For the ATREFanalysis of Example 47, 16 wt. % of the polymer was eluted below atemperature of 40° C., 27 wt. % of the polymer was eluted between 40° C.and 76° C., 2 wt. % was eluted between 76° C. and 86° C., and 55 wt. %was eluted above a temperature of 86° C.

TABLE I Examples 1-43. Example/ MET FSCA SA ZN Time Activity Description(g) (g) (g) (g) (min) PE (g/g/hr) 1 MET 1 + K 0.001 0.2 0.005 30 5025020 2 MET 1 + K 0.002 0.2 0.005 30 450 4500 3 MET 1 + K 0.002 0.2 0.00530 592 5920 4 MET 1 + K 0.002 0.2 0.005 30 435 4354 5 MET 1 + K 0.0010.2 0.005 30 204 2042 6 MET 1 + K 0.0005 0.2 0.005 30 144 1440 7 MET 1 +K 0.001 0.2 0.005 30 429 4290 8 MET 1 + K 0.001 0.2 0.005 30 97 970 9MET 1 + K 0.001 0.2 0.005 30 153 1530 10 MET 1 + K 0.002 0.2 0.005 30454 4540 11 MET 1 + K 0.002 0.2 0.005 30 247 2470 12 MET 2 + K 0.001 0.20.005 30 209 2090 13 MET 2 + K 0.002 0.2 0.005 30 230 2300 14 MET 2 + K0.002 0.2 0.005 30 81 810 15 MET 3 + K 0.001 0.2 0.005 30 280 2800 16MET 3 + K 0.002 0.2 0.005 30 410 4100 17 MET 3 + K 0.002 0.2 0.005 30394 3940 18 MET 3 + K 0.002 0.2 0.005 30 495 4950 19 MET 3 + K 0.002 0.20.005 30 566 5660 20 MET 1 + B 0.001 0.2 0.005 30 472 4720 21 MET 1 + B0.001 0.2 0.005 30 380 3800 22 MET 1 + B 0.001 0.2 0.005 30 540 5400 23MET 1 + B 0.001 0.2 0.005 30 308 3080 24 MET 1 + B 0.001 0.2 0.005 30355 3550 25 MET 1 + B 0.001 0.2 0.005 30 336 3360 26 MET 1 + B 0.001 0.20.005 30 685 6850 27 MET 1 + B 0.001 0.2 0.005 30 785 7850 28 MET 1 + B0.0005 0.2 0.005 30 194 1943 29 MET 1 + B 0.0005 0.2 0.005 30 156 156030 MET 1 + B 0.0005 0.2 0.005 30 342 3420 31 MET 1 + B 0.0005 0.2 0.00530 153 1530 32 MET 1 + B 0.0005 0.2 0.005 30 130 1300 33 MET 4 + B 0.0020.2 0.005 30 137 1370 34 MET 4 + B 0.002 0.2 0.005 30 174 1740 35 MET4 + B 0.002 0.2 0.005 30 108 1082 36 MET 4 + B 0.002 0.2 0.005 30 1341340 37 MET 4 + B 0.002 0.2 0.005 30 137 1370 38 MET 4 + B 0.002 0.20.005 30 95 950 39 MET 4 + B 0.002 0.2 0.005 30 103 1030 40 MET 4 + B0.002 0.2 0.005 30 71 710 41 MET 4 + B 0.002 0.2 0.005 30 150 1500 42MET 3 + B 0.002 0.2 0.005 30 147 1470 43 MET 3 + B 0.002 0.2 0.005 30686 6864

TABLE II Examples 1-43. Mn Mw Mz Mv Mp Ex. (kg/mol) (kg/mol) (kg/mol)(kg/mol) (kg/mol) Mw/Mn Mz/Mw η_(o) (Pa · s) Density MI HLMI 1 20.3 151695 119 65 7.45 4.60 2.17E+04 0.9576 0.32 19.6 2 27.0 198 899 156 807.32 4.55 4.94E+04 0.9551 0.16 9.5 3 13.0 152 663 119 65 11.72 4.352.48E+04 0.9544 0.32 28.9 4 26.5 178 694 143 84 6.72 3.90 4.35E+040.9546 0.22 15.2 5 23.6 203 808 161 89 8.61 3.98 6.42E+04 0.9546 0.0815.2 6 73.0 371 936 322 322 5.09 2.52 3.85E+05 0.3 7 37.5 182 534 153 994.85 2.93 5.71E+04 0.9125 0.14 6.3 8 52.4 385 1625 305 170 7.34 4.224.98E+05 0.9216 1.2 9 80.1 254 597 234 239 3.15 2.35 1.54E+05 0.9348 110 44.7 184 381 163 131 4.13 2.07 7.96E+04 0.9141 4.9 11 96.7 251 456228 245 2.59 1.82 1.35E+05 0.8910 0.9 12 25.0 246 1025 190 70 9.83 4.172.92E+05 0.9445 0.3 35.7 13 31.4 279 1319 212 75 8.91 4.73 3.08E+050.9541 0.45 62.4 14 20.8 68 170 60 53 3.27 2.50 9.97E+02 0.9354 10.2 1540.4 233 769 193 128 5.76 3.30 1.01E+05 0.9524 3.6 16 50.3 225 765 185109 4.47 3.40 7.62E+04 0.9538 0.07 6 17 52.8 328 1201 268 159 6.21 3.662.77E+05 0.9484 1.1 18 28.1 192 659 157 94 6.83 3.43 5.27E+04 0.95280.14 8.8 19 36.4 195 677 159 97 5.34 3.48 3.74E+04 0.9501 0.15 12.4 2043.2 234 638 198 115 5.42 2.72 1.01E+05 0.9131 4.4 21 77.9 246 487 220195 3.16 1.98 8.97E+04 0.8968 0.6 22 45.6 207 574 175 109 4.54 2.787.19E+04 0.9178 7.5 23 38.1 160 362 139 113 4.19 2.26 1.88E+04 0.91730.39 12.7 24 44.2 161 356 140 119 3.63 2.21 2.12E+04 0.9129 0.32 12.5 2574.4 273 609 240 195 3.67 2.23 1.24E+05 0.9112 1.3 26 65.8 219 468 193165 3.32 2.14 4.51E+04 0.9328 3.6 27 56.7 201 406 178 161 3.54 2.024.60E+04 0.9342 14.7 28 70.3 290 597 258 244 4.13 2.06 1.40E+05 1.6 2954.6 274 570 243 256 5.01 2.08 1.04E+05 1.4 30 63.6 248 557 219 184 3.902.24 8.62E+04 1.3 31 59.9 225 488 199 177 3.76 2.17 6.13E+04 2.4 32 62.6229 457 205 186 3.66 2.00 6.93E+04 0.13 2.9 33 8.7 56 248 44 26 6.404.47 6.19E+02 0.9061 34 20.8 85 309 70 46 4.11 3.61 7.79E+03 0.9225 358.7 62 329 47 28 7.11 5.33 3.48E+02 0.9166 36 11.7 43 135 37 31 3.713.12 1.13E+02 0.9067 37 6.6 46 255 36 23 7.06 5.50 1.01E+02 0.9150 15.138 9.8 30 59 27 26 3.06 1.95 4.77E+01 0.8950 39 31.2 387 3003 262 5112.41 7.75 2.44E+05 0.9403 40 15.6 157 1469 106 40 10.07 9.35 4.79E+050.9427 0.84 41 15.8 117 794 85 36 7.42 6.78 1.29E+06 0.9464 1.11 68.1 4231.9 342 1493 269 151 10.71 4.37 5.39E+05 0.9498 1.1 43 64.5 528 2117414 304 8.19 4.01 2.63E+06 0.9428 0.2

TABLE III Examples 45-47. Example/ SA ZN Time PE Activity DescriptionMET (g) (g) (g) (min) (g) (g/g/hr) 45 MET 1 + K 0.0012 0.12 0.0054 30233 3750 46 MET 1 + K 0.0013 0.12 0.0041 30 217 3580 47 MET 1 + K 0.00200.10 0.0038 30 196 3960

TABLE IV Examples 45-47. Mn Mw Mz Mv Mp Ex. (kg/mol) (kg/mol) (kg/mol)(kg/mol) (kg/mol) Mw/Mn Mz/Mw η_(o) (Pa · s) Density MI HLMI 45 25.5 150625 121 82 5.87 4.16 1.50E+04 0.920 0.71 16 46 20.6 142 516 115 77 6.923.63 1.31E+04 0.921 0.74 18 47 29.7 214 909 167 69 7.21 4.25 2.01E+040.915 0.50 14

The invention is described above with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the above detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A process to produce a catalyst composition, the processcomprising (a) contacting an activator-support and an organoaluminumcompound for a first period of time to form a precontacted mixture, and(b) contacting the precontacted mixture with a metallocene compound anda Ziegler-Natta component comprising titanium supported on MgCl₂ for asecond period of time to form the catalyst composition.

Aspect 2. The process defined in aspect 1, wherein the first period oftime is any suitable time period or in any range of first time periodsdisclosed herein, e.g., from about 10 sec to about 48 hr, from about 30sec to about 6 hr, at least about 5 sec, at least about 1 min, etc.

Aspect 3. The process defined in aspect 1 or 2, wherein the secondperiod of time is any suitable time period or in any range of secondtime periods disclosed herein, e.g., from about 1 sec to about 48 hr,from about 1 min to about 6 hr, at least about 5 min, at least about 10min, etc.

Aspect 4. A catalyst composition produced by the process defined in anyone of aspects 1-3.

Aspect 5. A catalyst composition comprising:

(A) a precontacted mixture comprising an activator-support and anorganoaluminum compound;

(B) a metallocene compound; and

(C) a Ziegler-Natta component comprising titanium supported on MgCl₂.

Aspect 6. The process or composition defined in any one of aspects 1-5,wherein an activity of the catalyst composition is greater (by anyamount disclosed herein, e.g., at least about 10%, at least about 25%,at least about 100%, etc.) than that of a catalyst system obtained byfirst combining the activator-support and the metallocene compound, andthen combining the organoaluminum compound and the Ziegler-Nattacomponent, under the same polymerization conditions.

Aspect 7. The process or composition defined in any one of aspects 1-6,wherein an activity of the catalyst composition is from about 15% toabout 1000% greater, or from about 25% to about 800% greater, etc., thanthat of a catalyst system obtained by first combining theactivator-support and the metallocene compound, and then combining theorganoaluminum compound and the Ziegler-Natta component, under the samepolymerization conditions.

Aspect 8. A process to produce a catalyst composition, the processcomprising contacting, in any order: (i) a metallocene compound, (ii) aZiegler-Natta component comprising titanium supported on MgCl₂, (iii) anactivator-support, and (iv) an organoaluminum compound, to form thecatalyst composition.

Aspect 9. The process defined in aspect 8, wherein the metallocenecompound, the Ziegler-Natta component, the activator-support, and theorganoaluminum compound are contacted for any time period sufficient toform the catalyst composition, e.g., from about 1 sec to about 48 hr,from about 30 sec to about 6 hr, at least about 5 sec, at least about 1min, etc.

Aspect 10. The process defined in aspect 8 or 9, wherein the metallocenecompound is present as a solution in any suitable non-polar hydrocarbonor any non-polar hydrocarbon disclosed herein, e.g., propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane,n-hexane, n-heptane, toluene, etc., or combinations thereof.

Aspect 11. A catalyst composition produced by the process defined in anyone of aspects 8-10.

Aspect 12. A catalyst composition comprising:

(i) a metallocene compound;

(ii) a Ziegler-Natta component comprising titanium supported on MgCl₂;

(iii) an activator-support; and

(iv) an organoaluminum compound.

Aspect 13. The process or composition defined in any one of precedingaspects, wherein the organoaluminum compound comprisestrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, or any combination thereof.

Aspect 14. The process or composition defined in any one of aspects1-13, wherein the organoaluminum compound comprises triethylaluminum.

Aspect 15. The process or composition defined in any one of aspects1-13, wherein the organoaluminum compound comprises triisobutylaluminum.

Aspect 16. The process or composition defined in any one of thepreceding aspects, wherein the catalyst composition is substantiallyfree of aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, or combinations thereof.

Aspect 17. The process or composition defined in any one of aspects1-16, wherein the activator-support comprises a solid oxide treated withan electron-withdrawing anion, for example, comprising any solid oxidetreated with any electron-withdrawing anion disclosed herein.

Aspect 18. The process or composition defined in aspect 17, wherein thesolid oxide comprises silica, alumina, silica-alumina, silica-coatedalumina, aluminum phosphate, aluminophosphate, heteropolytungstate,titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof,or any mixture thereof; and the electron-withdrawing anion comprisessulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, phospho-tungstate, or any combinationthereof.

Aspect 19. The process or composition defined in any one of aspects1-16, wherein the activator-support comprises a fluorided solid oxide, asulfated solid oxide, a phosphated solid oxide, or a combinationthereof.

Aspect 20. The process or composition defined in any one of aspects1-16, wherein the activator-support comprises fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, phosphatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, phosphated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, fluorided-chlorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof.

Aspect 21. The process or composition defined in any one of aspects1-16, wherein the activator-support comprises fluorided alumina,fluorided silica-alumina, fluorided silica-zirconia, fluoridedsilica-coated alumina, fluorided-chlorided silica-coated alumina, or anycombination thereof (e.g., fluorided-chlorided silica-coated alumina orfluorided silica-coated alumina).

Aspect 22. The process or composition defined in any one of aspects1-16, wherein the activator-support comprises sulfated alumina, sulfatedsilica-alumina, sulfated silica-coated alumina, or any combinationthereof (e.g., sulfated alumina).

Aspect 23. The process or composition defined in any one of aspects1-22, wherein the activator-support further comprises any metal or metalion disclosed herein, e.g., zinc, nickel, vanadium, titanium, silver,copper, gallium, tin, tungsten, molybdenum, zirconium, or anycombination thereof.

Aspect 24. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged metallocenecompound, e.g., any bridged metallocene compound disclosed herein.

Aspect 25. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconiumbased metallocene compound with a fluorenyl group, and with no arylgroups on the bridging group.

Aspect 26. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconiumbased metallocene compound with a cyclopentadienyl group and a fluorenylgroup, and with no aryl groups on the bridging group.

Aspect 27. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconium orhafnium based metallocene compound with a fluorenyl group, and an arylgroup on the bridging group.

Aspect 28. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconium orhafnium based metallocene compound with a cyclopentadienyl group andfluorenyl group, and an aryl group on the bridging group.

Aspect 29. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconiumbased metallocene compound with a fluorenyl group, and an aryl group onthe bridging group.

Aspect 30. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged hafnium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group.

Aspect 31. The process or composition defined in any one of aspects27-30, wherein the aryl group is a phenyl group.

Aspect 32. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconium orhafnium based metallocene compound with a cyclopentadienyl group and afluorenyl group, and with an alkenyl substituent.

Aspect 33. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconium orhafnium based metallocene compound with a cyclopentadienyl group and afluorenyl group, and with an alkenyl substituent on the bridging groupand/or on the cyclopentadienyl group.

Aspect 34. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconium orhafnium based metallocene compound with two indenyl groups.

Aspect 35. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises a bridged zirconiumbased metallocene compound with two indenyl groups.

Aspect 36. The process or composition defined in any one of aspects34-35, wherein the bridging group contains a silicon atom.

Aspect 37. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridgedmetallocene compound, e.g., any unbridged metallocene compound disclosedherein.

Aspect 38. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged zirconiumor hafnium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group.

Aspect 39. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged zirconiumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group.

Aspect 40. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged zirconiumbased metallocene compound containing two cyclopentadienyl groups.

Aspect 41. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged zirconiumbased metallocene compound containing two indenyl groups.

Aspect 42. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged zirconiumbased metallocene compound containing a cyclopentadienyl and an indenylgroup.

Aspect 43. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged zirconiumbased homodinuclear metallocene compound.

Aspect 44. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridged hafniumbased homodinuclear metallocene compound.

Aspect 45. The process or composition defined in any one of aspects1-23, wherein the metallocene compound comprises an unbridgedheterodinuclear metallocene compound.

Aspect 46. The process or composition defined in any one of thepreceding aspects, wherein a weight percentage of magnesium, based onthe weight of the Ziegler-Natta component, is any suitable amount or inany weight percentage range disclosed herein, e.g., from about 0.1 toabout 10 wt. %, from about 1 to about 8 wt. %, from about 3 to about 8wt. %, from about 4 to about 6 wt. %, etc.

Aspect 47. The process or composition defined in any one of thepreceding aspects, wherein a weight percentage of titanium, based on theweight of the Ziegler-Natta component, is any suitable amount or in anyweight percentage range disclosed herein, e.g., from about 0.1 to about10 wt. %, from about 1 to about 8 wt. %, from about 2 to about 7 wt. %,from about 3 to about 6 wt. %, etc.

Aspect 48. The process or composition defined in any one of thepreceding aspects, wherein the Ziegler-Natta component comprises anysuitable titanium compound disclosed herein, e.g., TiCl₃, TiCl₄, TiBr₄,TiI₄, TiF₄, titanium alkoxides, etc., as well as combinations thereof.

Aspect 49. The process or composition defined in any one of thepreceding aspects, wherein the Ziegler-Natta component further comprisespolyethylene, e.g., a pre-polymerized Ziegler-Natta component.

Aspect 50. The process or composition defined in any one of thepreceding aspects, wherein the weight ratio of the metallocene compoundto the activator-support is in any range of weight ratios disclosedherein, e.g., from about 1:1 to about 1:1,000,000, from about 1:10 toabout 1:10,000, or from about 1:20 to about 1:1000.

Aspect 51. The process or composition defined in any one of thepreceding aspects, wherein the weight ratio of the activator-support tothe organoaluminum compound is in any range of weight ratios disclosedherein, e.g., from about 1:5 to about 1000:1, from about 1:3 to about200:1, or from about 1:1 to about 100:1.

Aspect 52. The process or composition defined in any one of thepreceding aspects, wherein a molar ratio of the metallocene compound(e.g., Zr or Hf) to Ti in the catalyst composition is any suitable molarratio or in any range disclosed herein, e.g., from about 10:1 to about1:10, from about 5:1 to about 1:5, from about 3:1 to about 1:5, fromabout 3:1 to about 1:3, from about 2.8:1 to about 1:2.5, etc.

Aspect 53. The process or composition defined in any one of thepreceding aspects, wherein the catalyst composition has a catalystactivity in any range of catalyst activities disclosed herein, e.g.,greater than about 500 g/g/hr, greater than about 1,000 g/g/hr, greaterthan about 2,000 g/g/hr, greater than about 4,000 g/g/hr (grams ofpolymer per gram of activator-support per hour), etc.

Aspect 54. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of aspects 1-53with an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer.

Aspect 55. The process defined in aspect 54, wherein the olefin monomercomprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀ olefin.

Aspect 56. The process defined in aspect 54 or 55, wherein the olefinmonomer and the optional olefin comonomer independently comprise aC₂-C₂₀ alpha-olefin.

Aspect 57. The process defined in any one of aspects 54-56, wherein theolefin monomer comprises ethylene.

Aspect 58. The process defined in any one of aspects 54-57, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Aspect 59. The process defined in any one of aspects 54-58, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 60. The process defined in any one of aspects 54-56, wherein theolefin monomer comprises propylene.

Aspect 61. The process defined in any one of aspects 54-60, wherein thepolymerization reactor system comprises a batch reactor, a slurryreactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Aspect 62. The process defined in any one of aspects 54-61, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Aspect 63. The process defined in any one of aspects 54-62, wherein thepolymerization reactor system comprises a loop slurry reactor.

Aspect 64. The process defined in any one of aspects 54-63, wherein thepolymerization reactor system comprises a single reactor.

Aspect 65. The process defined in any one of aspects 54-63, wherein thepolymerization reactor system comprises 2 reactors.

Aspect 66. The process defined in any one of aspects 54-63, wherein thepolymerization reactor system comprises more than 2 reactors.

Aspect 67. The process defined in any one of aspects 54-66, wherein theolefin polymer comprises any olefin polymer disclosed herein.

Aspect 68. The process defined in any one of aspects 54-59 and 61-67,wherein the olefin polymer is an ethylene homopolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or anethylene/1-octene copolymer.

Aspect 69. The process defined in any one of aspects 54-59 and 61-67,wherein the olefin polymer is an ethylene/1-hexene copolymer.

Aspect 70. The process defined in any one of aspects 54-56 and 60-67,wherein the olefin polymer is a polypropylene homopolymer or apropylene-based copolymer.

Aspect 71. The process defined in any one of aspects 54-70, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 60° C. to about 120° C. and a reaction pressure ina range from about 200 to about 1000 psig (about 1.4 to about 6.9 MPa).

Aspect 72. The process defined in any one of aspects 54-71, wherein thepolymerization conditions are substantially constant, e.g., for aparticular polymer grade.

Aspect 73. The process defined in any one of aspects 54-72, wherein nohydrogen is added to the polymerization reactor system.

Aspect 74. The process defined in any one of aspects 54-72, whereinhydrogen is added to the polymerization reactor system.

Aspect 75. The process defined in any one of aspects 54-74, wherein theolefin polymer is characterized by any MI disclosed herein, and/or anyHLMI disclosed herein, and/or any density disclosed herein, and/or anyMn disclosed herein, and/or any Mw disclosed herein, and/or any Mzdisclosed herein, and/or any Mw/Mn disclosed herein, and/or any Mz/Mwdisclosed herein.

Aspect 76. The process defined in any one of aspects 54-75, wherein theolefin polymer has less than about 0.008 long chain branches (LCB) per1000 total carbon atoms, e.g., less than about 0.005 LCB, or less thanabout 0.003 LCB.

Aspect 77. The process defined in any one of aspects 54-76, wherein theolefin polymer has a decreasing or substantially flat short chain branchdistribution (SCBD), as determined by any procedure disclosed herein.

Aspect 78. The process defined in any one of aspects 54-77, wherein theolefin polymer has the following polymer fractions, as determined byATREF: less than about 4 wt. % of the polymer eluted below a temperatureof 40° C., from about 40 to about 62 wt. % of the polymer eluted between40 and 76° C., from about 2 to about 21 wt. % of the polymer elutedbetween 76 and 86° C., and from about 29 to about 40 wt. % of thepolymer eluted above a temperature of 86° C.

Aspect 79. The process defined in any one of aspects 54-77, wherein theolefin polymer has the following polymer fractions, as determined byATREF: from about 1 to about 18 wt. % (or from about 1 to about 16 wt.%, or from about 1 to about 8 wt. %) of the polymer eluted below atemperature of 40° C.; from about 1 to about 15 wt. % (or from about 1to about 10 wt. %, or from about 1 to about 8 wt. %) of the polymereluted between 76 and 86° C.; from about 27 to about 60 wt. % (or fromabout 29 to about 60 wt. %, or from about 28 to about 48 wt. %, or fromabout 29 to about 40 wt. %) of the polymer eluted above a temperature of86° C.; and the remaining percentage of the polymer (to reach 100 wt. %)eluted between 40 and 76° C.

Aspect 80. An olefin polymer produced by the polymerization processdefined in any one of aspects 54-79.

Aspect 81. An article comprising the olefin polymer defined in aspect80.

Aspect 82. A method or forming or preparing an article of manufacturecomprising an olefin polymer, the method comprising (i) performing theolefin polymerization process defined in any one of aspects 54-79 toproduce the olefin polymer, and (ii) forming the article of manufacturecomprising the olefin polymer, e.g., via any technique disclosed herein.

Aspect 83. The article defined in aspect 81 or 82, wherein the articleis an agricultural film, an automobile part, a bottle, a drum, a fiberor fabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, or atoy.

We claim:
 1. An ethylene copolymer characterized by: a melt index ofless than or equal to about 10 g/10 min; a density in a range from about0.90 g/cm³ to about 0.935 g/cm³; less than or about 0.01 long chainbranches per 1000 total carbon atoms; and a ratio of Mw/Mn in a rangefrom about 2.5 to about 8; and having the following polymer fractions inan ATREF test: from about 1 to about 18 wt. % of the polymer elutedbelow a temperature of 40° C.; from about 1 to about 10 wt. % of thepolymer eluted between 76 and 86° C.; from about 27 to about 60 wt. % ofthe polymer eluted above a temperature of 86° C.; and the remainingpercentage of the polymer eluted between 40 and 76° C.
 2. The copolymerof claim 1, wherein the copolymer is characterized by: a melt index ofless than or equal to about 2 g/10 min; a density in a range from about0.91 g/cm³ to about 0.93 g/cm³; and a ratio of Mw/Mn in a range fromabout 2.5 to about
 7. 3. The copolymer of claim 1, wherein the copolymerhas the following polymer fractions in an ATREF test: from about 1 toabout 8 wt. % of the polymer eluted below a temperature of 40° C.; fromabout 1 to about 8 wt. % of the polymer eluted between 76 and 86° C.;from about 28 to about 48 wt. % of the polymer eluted above atemperature of 86° C.; and the remaining percentage of the polymereluted between 40 and 76° C.
 4. The copolymer of claim 1, wherein thecopolymer has a high load melt index in a range from about 2 to about 40g/10 min.
 5. The copolymer of claim 1, wherein the copolymer has lessthan about 0.008 long chain branches per 1000 total carbon atoms.
 6. Thecopolymer of claim 1, wherein the copolymer has a substantially constantshort chain branch distribution.
 7. The copolymer of claim 1, whereinthe ethylene copolymer comprises an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer, and ischaracterized by a Mw in a range from about 120,000 to about 260,000g/mol.
 8. An article of manufacture comprising the copolymer of claim 1.9. The copolymer of claim 1, wherein: a number of short chain branchesper 1000 total carbon atoms of the copolymer at Mz is less than at Mn;and the copolymer comprises an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.
 10. Anethylene copolymer characterized by: a melt index of less than or equalto about 10 g/10 min; a density in a range from about 0.90 g/cm³ toabout 0.935 g/cm³; a Mw in a range from about 100,000 to about 300,000g/mol; and a ratio of Mw/Mn in a range from about 2.5 to about 8; andhaving the following polymer fractions in an ATREF test: from about 1 toabout 8 wt. % of the polymer eluted below a temperature of 40° C.; fromabout 1 to about 15 wt. % of the polymer eluted between 76 and 86° C.;from about 27 to about 60 wt. % of the polymer eluted above atemperature of 86° C.; and the remaining percentage of the polymereluted between 40 and 76° C.
 11. The copolymer of claim 10, wherein theethylene copolymer comprises an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.
 12. Thecopolymer of claim 11, wherein the copolymer is characterized by: a meltindex of less than or equal to about 2 g/10 min; a density in a rangefrom about 0.91 g/cm³ to about 0.93 g/cm³; and a ratio of Mw/Mn in arange from about 2.5 to about
 7. 13. An article of manufacturecomprising the copolymer of claim
 11. 14. The copolymer of claim 10,wherein the copolymer has the following polymer fractions in an ATREFtest: from about 1 to about 8 wt. % of the polymer eluted below atemperature of 40° C.; from about 1 to about 10 wt. % of the polymereluted between 76 and 86° C.; from about 28 to about 48 wt. % of thepolymer eluted above a temperature of 86° C.; and the remainingpercentage of the polymer eluted between 40 and 76° C.
 15. The copolymerof claim 14, wherein the copolymer has a high load melt index in a rangefrom about 2 to about 40 g/10 min.
 16. The copolymer of claim 15,wherein the ethylene copolymer comprises an ethylene/1-butene copolymer,an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer. 17.The copolymer of claim 16, wherein the ethylene copolymer ischaracterized by a Mw in a range from about 120,000 to about 260,000g/mol, and from about 1 to about 8 wt. % of the polymer is elutedbetween 76 and 86° C.
 18. The copolymer of claim 10, wherein thecopolymer has less than about 0.008 long chain branches per 1000 totalcarbon atoms.
 19. The copolymer of claim 10, wherein the copolymer has asubstantially constant short chain branch distribution.
 20. Thecopolymer of claim 10, wherein a number of short chain branches per 1000total carbon atoms of the copolymer at Mz is less than at Mn.
 21. Thecopolymer of claim 10, wherein the copolymer has the following polymerfractions in an ATREF test: from about 1 to about 8 wt. % of the polymereluted below a temperature of 40° C.; from about 1 to about 10 wt. % ofthe polymer eluted between 76 and 86° C.; from about 29 to about 40 wt.% of the polymer eluted above a temperature of 86° C.; and the remainingpercentage of the polymer eluted between 40 and 76° C.
 22. The copolymerof claim 21, wherein from about 1 to about 8 wt. % of the polymer iseluted between 76 and 86° C.